U.S. patent application number 12/288062 was filed with the patent office on 2009-04-23 for adhesion promoting photoinitiators for uv cured coatings over metal surfaces.
Invention is credited to Ying Dong, Dante A. Galan, James P. Galbo, Eugene V. Sitzmann.
Application Number | 20090104464 12/288062 |
Document ID | / |
Family ID | 40229708 |
Filed Date | 2009-04-23 |
United States Patent
Application |
20090104464 |
Kind Code |
A1 |
Galbo; James P. ; et
al. |
April 23, 2009 |
Adhesion promoting photoinitiators for UV cured coatings over metal
surfaces
Abstract
Compounds containing both photoinitiator moieties and adhesion
promoting moieties and coating formulations containing them are
disclosed, in particular, durable UV cured primer layers for coil
coatings. One embodiment includes a coated metal surface which
comprises a metal substrate with at least one surface immediately
adjacent to a coating layer comprising a photoinitiator chemically
bound to an adhesion promoter is disclosed.
Inventors: |
Galbo; James P.; (Wingdale,
NY) ; Dong; Ying; (Tarrytown, NY) ; Galan;
Dante A.; (Corona, NY) ; Sitzmann; Eugene V.;
(Newark, DE) |
Correspondence
Address: |
JoAnn Villamizar;Ciba Corporation/Patent Department
540 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Family ID: |
40229708 |
Appl. No.: |
12/288062 |
Filed: |
October 16, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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60999361 |
Oct 17, 2007 |
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|
Current U.S.
Class: |
428/461 ; 522/33;
522/43; 549/560; 556/437; 560/85; 562/464; 564/349 |
Current CPC
Class: |
C07C 2601/14 20170501;
C07F 7/1804 20130101; C07C 235/82 20130101; C08F 2/50 20130101;
Y10T 428/31692 20150401; C07C 59/90 20130101; C07C 69/76 20130101;
C07C 217/28 20130101 |
Class at
Publication: |
428/461 ;
549/560; 564/349; 562/464; 560/85; 556/437; 522/43; 522/33 |
International
Class: |
B32B 15/085 20060101
B32B015/085; C07D 303/12 20060101 C07D303/12; C07C 215/20 20060101
C07C215/20; C07C 65/32 20060101 C07C065/32; C07C 69/76 20060101
C07C069/76; C07F 7/04 20060101 C07F007/04; C08F 2/46 20060101
C08F002/46 |
Claims
1) A coated metal surface which comprises a) a metal with at least
one surface which is immediately adjacent to a coating layer which
coating layer comprises b) one or more one or more ethylenically
unsaturated monomers, oligomers or prepolymers, and c) from about
0.05 to about 25% by weight, based on the total weight of the
coating layer solids, of one or more compounds of the formulae:
##STR00056## Wherein G.sub.1 is --H, glycidyl,
--CH.sub.2--CH(OH)--CH--NR.sub.4R.sub.6,
--CH(CH.sub.2OH)--CH--NR.sub.4R.sub.6 or --CH.sub.2--CH(OH)--CH--N
R.sub.4R.sub.6, G.sub.2 and G.sub.3 are, independently,
C.sub.1-C.sub.4 alkyl, or taken together, pentamethylene, R is
C.sub.1-C.sub.6 alkylene, C.sub.1-C.sub.6 alkylene-oxy,
C.sub.4-C.sub.6 alkylene interrupted by 1 or 2 oxygen atoms or
C.sub.4-C.sub.6 alkene-oxy interrupted by 1 or 2 oxygen atoms A is
a group selected from --(O).sub.s--C(.dbd.O)G,
--O--CH.sub.2--C(.dbd.O)G,
--(O).sub.s--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--(O).sub.s--Si(OR.sub.2).sub.2OR.sub.3, ##STR00057## s is 0 or 1,
n is 0, 1 or 2 L is a direct bond, --CH.sub.2-- or
--CH(CH.sub.3)--, G is selected from OH, ##STR00058##
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--R.sub.7--CH.sub.2N(R.sub.8).sub.p--(CH.sub.2).sub.3--Si--(OR.sub.2).sub-
.2OR.sub.3, --R.sub.10--C(.dbd.O)--OH, phenyl or naphthyl, each
being substituted by one to three --COOH, or one or two
--C(.dbd.O)--O--CH2-C(CH.sub.3)(CH.sub.2OH)--COOH and, optionally
by --(C.dbd.O)--O-Z or one or two --COO--R.sub.11 or
--COO--(R.sub.4--O).sub.x--H, where R.sub.4is not --H, and x is
1-3; phenyl or naphthyl, each being substituted by one or two
--(C.dbd.O)--N(R.sub.15).sub.p(R.sub.16).sub.2-p and optionally
substituted by --(C.dbd.O)--O-Z, where p is 0 or 1, R.sub.15 is
--H, C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and R.sub.16 is
C.sub.1-C.sub.4 hydroxyalkyl or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3; and phenyl
substituted at the 2 position by a group C(.dbd.O)OH and at the 4
or 5 position by a group ##STR00059## wherein G.sub.4 is a direct
bond or --(C.dbd.O)--, one of G.sub.7 or G.sub.8 is --H, the other
is --H, -Z, or --R.sub.11, R.sub.11 is C.sub.1-C.sub.4 alkyl,
C.sub.3-C.sub.4 alkenyl, or C.sub.3-C.sub.6 alkyl interrupted by 1
or 2 --O--, and wherein R.sub.11 is optionally substituted on a
saturated carbon atom by --OH with the proviso that the
substitution does not form an acetal X is
O--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--N(R.sub.5).sub.p(R.sub.6).sub.2-p, p is 0 or 1, Z is ##STR00060##
Y is --H or --(C.dbd.O)--C(G.sub.1)(G.sub.2)-OG.sub.1, R.sub.2 and
R.sub.3 are, independently, --H or C.sub.1-C.sub.4 alkyl, or
R.sub.3 is -Z, R.sub.4 is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.5 is --H,
C.sub.1-C.sub.4 alkyl, --CH.sub.2--CH(OH)--CH.sub.2--O-Z,
--CH(CH.sub.2OH)--CH.sub.2--O-Z, --CH.sub.2--CH(OZ)-CH.sub.2--OH,
or --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3; R.sub.6 is
C.sub.1-C.sub.4 alkyl substituted by OH or COOH, or R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.7 is
--CH.sub.2-- or --CH(CH.sub.3)--, R.sub.8 is --H, C.sub.1-C.sub.4
alkyl, --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3; R.sub.9 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where R.sub.2 and
R.sub.3 are methyl or ethyl, R.sub.10 is C.sub.2-C.sub.6 alkylene,
alkenylene, or alkylene substituted by
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, or R.sub.10 is
norbornylene, D is AR-- or ##STR00061##
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8).sub.p(R.sub.9).sub.2-p,
p is 0 or 1 --O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH, and A.sub.1 is
--OH, or --NR.sub.12R.sub.13, where R.sub.12 is --H,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkyl substituted by --OH or
--COOH, or --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.14, where
R.sub.14 is --H or C.sub.1-C.sub.4 alkyl, and R.sub.13 is
C.sub.1-C.sub.4 alkyl substituted by --OH or --COOH, or R.sub.13 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.14.
2) A coated metal surface according to claim 1 wherein the metal of
component a) is steel or aluminum.
3) A coated metal surface according to claim 1, wherein component
b) comprises one or more acrylate monomers, oligomers or
prepolymers.
4) A coated metal surface according to claim 1 wherein in component
c) R is C.sub.1-C.sub.6 alkylene, C.sub.2-C.sub.6 alkylene-oxy,
C.sub.4-C.sub.6 alkylene interrupted by 1 or 2 oxygen atoms, or
C.sub.4-C.sub.6 alkylene-oxy interrupted by 1 or 2 oxygen atoms or
AR-- taken together is a group --O--CH.sub.2--C(.dbd.O)G,
--O--CH.sub.2--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--O--CH.sub.2--Si(OR.sub.2).sub.2OZ, or ##STR00062## With the
proviso that in Formula I A is not --P(.dbd.O)(OH).sub.2 or
--Si(OR.sub.2).sub.2OR.sub.3, unless R.sub.3 is Z; and also in
Formula (I) AR is not --O--(CH2).sub.1-6--COOH,
--(CH.sub.2).sub.1-6--COOH,
--O--(CH.sub.2).sub.1-6--O--CH.sub.2--COOH,
--(CH.sub.2).sub.1-6--O--CH.sub.2--COOH,
O--(CH.sub.2).sub.2--O--Si(OR.sub.2).sub.2OR.sub.3, unless R.sub.3
is Z,
O--(CH.sub.2).sub.2--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.-
2).sub.2OR.sub.3, unless R.sub.3 is Z
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH when R is alkylene-oxy or
alkylene-oxy interrupted by oxygen atoms and R.sub.10 is
--CH.sub.2CH.sub.2-, --CH.dbd.CH--, or --CH.dbd.CH-- substituted by
once or twice by --CH.sub.3, or
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH when R is alkylene or
alkylene interrupted by oxygen atoms and R.sub.1 and R.sub.10
combined contain up to 8 saturated carbon atoms; and in Formula II
when Y is --(C.dbd.O)--C(G.sub.1)(G.sub.2)-OH, D is not
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3
where R.sub.4 is --H or C.sub.1-C.sub.4 alkyl, unless R.sub.3 is
-Z. and in Formula III A.sub.1 is not --COOH, or
--NR.sub.12R.sub.13 where R.sub.12 is --H and R.sub.13 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3, except where
R.sub.3 is -Z.
5) A coated metal surface according to claim 4 wherein G.sub.1 is
H, G.sub.2 and G.sub.3 are each methyl or pentamethylene, R is
C.sub.2-C.sub.6 alkylene or C.sub.2-C.sub.6 alkylene-oxy, A is a
group selected from --O--C(.dbd.O)G, --C(.dbd.O)G,
--O--(CH.sub.2).sub.2--C(.dbd.O)G, ##STR00063## G is selected from
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.4
is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--R.sub.7--CH.sub.2N(R.sub.8).sub.p--(CH.sub.2).sub.3--Si--(OR.sub.2).sub-
.2OR.sub.3, R.sub.8 is --H, C.sub.1-C.sub.4 alkyl,
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3; R.sub.7 is
--CH.sub.2-- or --CH(CH.sub.3)--, --R.sub.10--C(.dbd.O)--OH,
R.sub.10 is C.sub.2-C.sub.6 alkylene, alkenylene, or alkylene
substituted by --(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, or
R.sub.10 is norbornylene, phenyl substituted by two --COOH, and,
optionally by --(C.dbd.O)--O-Z; phenyl, substituted by
--(C.dbd.O)--N(R.sub.15).sub.p(R.sub.16).sub.2-p and optionally
substituted by --(C.dbd.O)--O-Z, where p is 0 or 1, R.sub.15 is
--H, C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and R.sub.16 is
C.sub.1-C.sub.4 hydroxyalkyl or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3; X is
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.4
is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--N(R.sub.5).sub.p(R.sub.6).sub.2-p, p is 0 or 1, R.sub.5 is --H,
C.sub.1-C.sub.4 alkyl, --CH.sub.2--CH(OH)--CH.sub.2--O-Z,
--CH(CH.sub.2OH)--CH.sub.2--O-Z, or
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3; R.sub.6 is
C.sub.1-C.sub.4 alkyl substituted by OH or COOH, or R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3; in Formula II, When
Y is H, D is --(CH.sub.2).sub.1-6COOH,
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
where R.sub.4 is --H or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.2 is methyl
or ethyl, and R.sub.3 is --H, methyl, or ethyl, or
--O--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), wherein
R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH or each of R.sub.5 and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH and when Y is
--(C.dbd.O)--C(CH.sub.3).sub.2--OH, D is
--O--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), wherein
R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH or each of R.sub.5 and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH and in Formula (III), A.sub.1 is
--NR.sub.12R.sub.13 where R.sub.12 and R.sub.13 are each
--CH.sub.2CH.sub.2--OH or R.sub.12 is H and R.sub.13is
--CH.sub.2CH.sub.2--OH or --CH.sub.2CH.sub.2CH.sub.2--OH.
6) A coated metal surface according to claim 1 wherein component c)
comprises a compound of the formula ##STR00064## ##STR00065##
wherein A is
--O--CH.sub.2--CH(OH)--CH.sub.2--N(CH.sub.2CH.sub.2OH).sub.2,
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH, R.sub.10 is
--CH.sub.2CH.sub.2-- substituted by either
--(CH.sub.2).sub.3--Si--(OCH.sub.3).sub.3 or
--(CH.sub.2).sub.3--Si--(OCH.sub.2CH.sub.3).sub.3,
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8)(R.sub.9), R.sub.8 is
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z where R.sub.7 is --CH.sub.2--,
R.sub.9 is --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where
R.sub.2 and R.sub.3 are methyl or ethyl, or A is
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8)(R.sub.9), R.sub.8 is
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3 or
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3, where R.sub.7
is --CH.sub.2--, R.sub.9 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where R.sub.2 is
methyl or ethyl and R.sub.3 is -Z, D' is
--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
where R.sub.4 is --H or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.2 is methyl
or ethyl, and R.sub.3 is --H, methyl, or ethyl, or
--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), R.sub.5 is H and
R.sub.6 is --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or
C.sub.2-C.sub.4 alkyl substituted by --OH or each or R.sub.5 and
R.sub.6 is --(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or
C.sub.2-C.sub.4 alkyl substituted by --OH.
7) A coated metal surface according to claim 1 wherein component c)
comprises a compound of the formula ##STR00066## wherein R.sub.12
and R.sub.13 are each --CH.sub.2CH.sub.2--OH or R.sub.12 is H and
R.sub.13 is --CH.sub.2CH.sub.2--OH or
--CH.sub.2CH.sub.2CH.sub.2--OH.
8) A coated metal surface according to claim 1 wherein component c)
comprises a compound of the formula ##STR00067## wherein Z is
##STR00068## G.sub.2 and G.sub.3 are methyl or taken together,
pentamethylene, G.sub.4 is a direct bond or --(C.dbd.O)--, and one
of G.sub.7 or G.sub.8 is --H, the other is --H or -Z.
9) A coated metal surface according to claim 1 which also comprises
5-25 weight percent, based on total solids, of an additional
photoinitiator or photoinitiator blend.
10) A coated metal surface according to claim 9, wherein the
additional photoinitiator or photoinitiator blend comprises one or
more compounds selected from phenyl
bis(2,4,6-trimethylbenzoyl)phosphine oxide,
2-hydroxy-2-methyl-1-phenyl-1-propanone,
2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpro-
pan-1-one,
2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one,
benzophenone and 1-hydroxycyclohexyl phenyl ketone.
11) A coated metal surface according to claim 10, wherein the
additional photoinitiator or photoinitiator blend comprises one or
more compounds or blends selected from a blend of 20% by weight
phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and 80% by weight
2-hydroxy-2-methyl-1-phenyl-1-propanone;
2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpro-
pan-1-one;
2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one; a
blend of 50 weight % benzophenone and 50 weight %
1-hydroxycyclohexyl phenyl ketone; Phenyl
bis(2,4,6-trimethylbenzoyl)phosphine oxide; 1-Hydroxycyclohexyl
phenyl ketone; and 2-Hydroxy-2-methyl-1-phenyl propan-1-one.
12) A coated metal surface according to claim 9, wherein the
additional photoinitiator or photoinitiator blend comprises the
blend 50 weight % benzophenone and 50 weight % 1-hydroxycyclohexyl
phenyl ketone or the compound phenyl
bis(2,4,6-trimethylbenzoyl)phosphine oxide.
13) A compound of the formulae: ##STR00069## Wherein G.sub.1 is
--H, glycidyl, --CH.sub.2--CH(OH)--CH--NR.sub.4R.sub.6,
--CH(CH.sub.2OH)--CH--NR.sub.4R.sub.6 or
--CH.sub.2--CH(OH)--CH--NR.sub.4R.sub.6, G.sub.2 and G.sub.3 are,
independently, C.sub.1-C.sub.4 alkyl, or taken together,
pentamethylene, R is C.sub.1-C.sub.6 alkylene, C.sub.2-C.sub.6
alkylene-oxy, C.sub.4-C.sub.6 alkylene interrupted by 1 or 2 oxygen
atoms, or C.sub.4-C.sub.6 alkylene-oxy interrupted by 1 or 2 oxygen
atoms or AR-- taken together is a group --O--CH.sub.2--C(.dbd.O)G,
--O--CH.sub.2--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--O--CH.sub.2--Si(OR.sub.2).sub.2OZ, or ##STR00070## A is a group
selected from --(O).sub.s--C(.dbd.O)G, --O--CH.sub.2--C(.dbd.O)G,
--(O).sub.s--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--(O).sub.s--Si(OR.sub.2).sub.2OR.sub.3, ##STR00071## s is 0 or 1,
n is 0, 1 or 2 and L is a direct bond, --CH.sub.2-- or
--CH(CH.sub.3)--, G is selected from OH, ##STR00072##
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--R.sub.7--CH.sub.2N(R.sub.8).sub.p--(CH.sub.2).sub.3--Si--(OR.sub.2).sub-
.2OR.sub.3, --R.sub.10--C(.dbd.O)--OH, phenyl or naphthyl, each
being substituted by one to three --COOH, or one or two
--C(.dbd.O)--O--CH2-C(CH.sub.3)(CH.sub.2OH)--COOH and, optionally
by --(C.dbd.O)--O-Z or one or two --COO--R.sub.11 or
--COO--(R.sub.4--O).sub.x--H, where R.sub.4 is not --H, and x is
1-3, phenyl or naphthyl, each being substituted by one or two
--(C.dbd.O)--N(R.sub.15).sub.p(R.sub.16).sub.2-p and optionally
substituted by --(C.dbd.O)--O-Z, where p is 0 or 1, R.sub.15 is
--H, C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and R.sub.16 is
C.sub.1-C.sub.4 hydroxyalkyl or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and phenyl
substituted at the 2 position by a group C(.dbd.O)OH and at the 4
or 5 position by a group ##STR00073## wherein G.sub.4 is a direct
bond or --(C.dbd.O)--, one of G.sub.7 or G.sub.8 is --H, the other
is --H, -Z, or --R.sub.11, R.sub.11 is C.sub.1-C.sub.4 alkyl,
C.sub.3-C.sub.4 alkenyl, or C.sub.3-C.sub.6 alkyl interrupted by 1
or 2 --O--, and wherein R.sub.11 is optionally substituted on a
saturated carbon atom by --OH with the proviso that the
substitution does not form an acetal X is
O--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--N(R.sub.5).sub.p(R.sub.6).sub.2-p, p is 0 or 1, Z is ##STR00074##
Y is --H or --(C.dbd.O)--C(G.sub.1)(G.sub.2)-OG.sub.1, R.sub.2 and
R.sub.3 are, independently, --H or C.sub.1-C.sub.4 alkyl, or
R.sub.3 is -Z, R.sub.4 is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.5 is --H,
C.sub.1-C.sub.4 alkyl, --CH.sub.2--CH(OH)--CH.sub.2--O-Z,
--CH(CH.sub.2OH)--CH.sub.2--O-Z, or
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3; R.sub.6 is
C.sub.1-C.sub.4 alkyl substituted by OH or COOH, or R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.7 is
--CH.sub.2-- or --CH(CH.sub.3)--, R.sub.8 is --H, C.sub.1-C.sub.4
alkyl, --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3; R.sub.9 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where R.sub.2 and
R.sub.3 are methyl or ethyl, R.sub.10 is C.sub.2-C.sub.6 alkylene,
alkenylene, or alkylene substituted by
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, or R.sub.10 is
norbornylene, D is AR-- or ##STR00075##
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8).sub.p(R.sub.9).sub.2-p,
p is 0 or 1 --O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH, q is 0, 1 or 2
and A.sub.1 is --OH, or --NR.sub.12R.sub.13, where R.sub.12 is --H,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkyl substituted by --OH or
--COOH, or --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.14, where
R.sub.14 is --H or C.sub.1-C.sub.4 alkyl, and R.sub.13 is
C.sub.1-C.sub.4 alkyl substituted by --OH or --COOH, or R.sub.13 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.14. R is
C.sub.1-C.sub.6 alkylene, C.sub.2-C.sub.6 alkylene-oxy,
C.sub.4-C.sub.6 alkylene interrupted by 1 or 2 oxygen atoms, or
C.sub.4-C.sub.6 alkylene-oxy interrupted by 1 or 2 oxygen atoms or
AR-- taken together is a group --O--CH.sub.2--C(.dbd.O)G,
--O--CH.sub.2--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--O--CH.sub.2--Si(OR.sub.2).sub.2OZ, or ##STR00076## With the
proviso that in Formula I A is not --P(.dbd.O)(OH).sub.2 or
--Si(OR.sub.2).sub.2OR.sub.3, unless R.sub.3 is Z; and also in
Formula I AR is not --O--(CH2).sub.1-6--COOH,
--(CH.sub.2).sub.1-6--COOH,
--O--(CH.sub.2).sub.1-6--O--CH.sub.2--COOH,
--(CH.sub.2).sub.1-6--O--CH.sub.2--COOH,
O--(CH.sub.2).sub.2--O--Si(OR.sub.2).sub.2OR.sub.3, unless R.sub.3
is Z,
O--(CH.sub.2).sub.2--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.-
2).sub.2OR.sub.3, unless R.sub.3 is Z
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH when R is alkylene-oxy or
alkylene-oxy interrupted by oxygen atoms and R.sub.10 is
--CH.sub.2CH.sub.2-, --CH.dbd.CH--, or --CH.dbd.CH-- substituted by
once or twice by --CH.sub.3, or
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH when R is alkylene or
alkylene interrupted by oxygen atoms and R.sub.1 and R.sub.10
combined contain up to 8 saturated carbon atoms; and in Formula II
when Y is --(C.dbd.O)--C(G.sub.1)(G.sub.2)-OH, D is not
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3
where R.sub.4 is --H or C.sub.1-C.sub.4 alkyl, unless R.sub.3 is
-Z. and in Formula III A.sub.1 is not --COOH, or
--NR.sub.12R.sub.13 where R.sub.12 is --H and R.sub.13 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3, except where
R.sub.3 is -Z.
14) A compound according to claim 13 wherein G.sub.1 is H, G.sub.2
and G.sub.3 are each methyl or pentamethylene, R is C.sub.2-C.sub.6
alkylene or C.sub.2-C.sub.6 alkylene-oxy, A is a group selected
from --O--C(.dbd.O)G, --C(.dbd.O)G,
--O--(CH.sub.2).sub.2--C(.dbd.O)G, ##STR00077## G is selected from
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.4
is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--R.sub.7--CH.sub.2N(R.sub.8).sub.p--(CH.sub.2).sub.3--Si--(OR.sub.2).sub-
.2OR.sub.3, R.sub.8 is --H, C.sub.1-C.sub.4 alkyl,
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3; R.sub.7 is
--CH.sub.2-- or --CH(CH.sub.3)--, --R.sub.10--C(.dbd.O)--OH,
R.sub.10 is C.sub.2-C.sub.6 alkylene, alkenylene, or alkylene
substituted by --(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, or
R.sub.10 is norbornylene, phenyl substituted by two --COOH, and,
optionally by --(C.dbd.O)--O-Z; phenyl, substituted by
--(C.dbd.O)--N(R.sub.15).sub.p(R.sub.16).sub.2-p and optionally
substituted by --(C.dbd.O)--O-Z, where p is 0 or 1, R.sub.15 is
--H, C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and R.sub.16 is
C.sub.1-C.sub.4 hydroxyalkyl or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3; X is
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.4
is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--N(R.sub.5).sub.p(R.sub.6).sub.2-p, p is 0 or 1, R.sub.5 is --H,
C.sub.1-C.sub.4 alkyl, --CH.sub.2--CH(OH)--CH.sub.2--O-Z,
--CH(CH.sub.2OH)--CH.sub.2--O-Z, or
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3; R.sub.6 is
C.sub.1-C.sub.4 alkyl substituted by OH or COOH, or R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3; in Formula II, when
Y is H, D is --(CH.sub.2).sub.1-6COOH,
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
where R.sub.4 is --H or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.2 is methyl
or ethyl, and R.sub.3 is --H, methyl, or ethyl, or
--O--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), wherein
R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH or each of R.sub.5 and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH and when Y is
--(C.dbd.O)--C(CH.sub.3).sub.2--OH, D is
--O--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), wherein
R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH or each of R.sub.5 and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH and in Formula III, A.sub.1 is
--NR.sub.12R.sub.13 where R.sub.12 and R.sub.13 are each
--CH.sub.2CH.sub.2--OH or R.sub.12 is H and R.sub.13 is
--CH.sub.2CH.sub.2--OH or --CH.sub.2CH.sub.2CH.sub.2--OH.
15) A compound according to claim 13 of the formula ##STR00078##
##STR00079## wherein A is
--O--CH.sub.2--CH(OH)--CH.sub.2--N(CH.sub.2CH.sub.2OH).sub.2,
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH, R.sub.10 is
--CH.sub.2CH.sub.2-- substituted by either
--(CH.sub.2).sub.3--Si--(OCH.sub.3).sub.3 or
--(CH.sub.2).sub.3--Si--(OCH.sub.2CH.sub.3).sub.3,
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8)(R.sub.9), R.sub.8 is
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z where R.sub.7 is --CH.sub.2--,
R.sub.9 is --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where
R.sub.2 and R.sub.3 are methyl or ethyl, or A is
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8)(R.sub.9), R.sub.8 is
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3 or
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3, where R.sub.7
is --CH.sub.2--, R.sub.9 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where R.sub.2 is
methyl or ethyl and R.sub.3 is -Z, D' is
--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
where R.sub.4 is --H or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.2 is methyl
or ethyl, and R.sub.3 is --H, methyl, or ethyl, or
--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), R.sub.5 is H and
R.sub.6 is --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or
C.sub.2-C.sub.4 alkyl substituted by --OH or each of R.sub.5 and
R.sub.6 is --(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or
C.sub.2-C.sub.4 alkyl substituted by --OH.
16) A compound according to claim 14 of the formula ##STR00080##
wherein R.sub.12 and R.sub.13 are each --CH.sub.2CH.sub.2--OH or
R.sub.12 is H and R.sub.13 is --CH.sub.2CH.sub.2--OH or
--CH.sub.2CH.sub.2CH.sub.2--OH.
17) A compound according to claim 13 of the formula ##STR00081##
wherein Z is ##STR00082## G.sub.2 and G.sub.3 are methyl or taken
together, pentamethylene, G.sub.4 is a direct bond or
--(C.dbd.O)--, and one of G.sub.7 or G.sub.8 is --H, the other is
--H or -Z.
18) A compound according to claim 13 of the formula ##STR00083##
##STR00084##
19) A composition comprising (b) at least one ethylenically
unsaturated compound, for example, an acrylate or amino acrylate,
(c) a photoinitiator of formula I, II or III according to claim 13,
(d) optionally, further photoinitiators and coinitiators (e)
optionally a film-forming binder based on a thermoplastic or
thermocurable resin; (f) optionally, further additives.
20) A composition according to claim 19 which is in direct contact
with a metal surface.
Description
[0001] This application claims benefit under 35 USC 119(e) of U.S.
provisional application No. 60/999,361, filed Oct. 17, 2007, the
disclosure of which is incorporated herein in its entirety by
reference.
[0002] Compounds that contain both photoinitiator moieties and
adhesion promoting moieties are provided which are used to generate
a more durable UV cured primer layer for coatings over metal
applications, for example, UV cured coil coatings. Also provided
are coating compositions which comprise said compounds and an
ethylenically unsaturated species, such as an acrylate resin or
monomer, and optionally binder polymers and other components. For
example, a coated metal surface which comprises a metal substrate
with at least one surface immediately adjacent to a coating layer
comprising a photoinitiator chemically bound to an adhesion
promoter is disclosed.
[0003] UV cured coil coatings offer energy saving advantages over
conventional thermally cured systems by making it possible to use
very high line speeds at ambient temperature. While thermal curing
may use a dwell time of 30 seconds in a 280 degree Celsius oven, UV
curing can occur in one second as the coating formulation passes
under a lamp at high speed. From an environmental perspective, UV
cured coil coatings use much less solvent than conventional
thermally cured resins.
[0004] Coil coating involves the application of an organic resin to
a flat metal surface. The metal is, for example, aluminum or steel.
In the process, a coil of metal is unwound, cleaned, treated,
primed, cured, treated with a top coat, cured and rewound. When the
metal roll reaches the customer, it is uncoiled and fashioned into
the end product. The end product is, for example, a roof or
building facade, office furniture, filing cabinets, appliances, or
the hood or door of a car. The severe stress that is placed upon
the coil coating as it is rolled for storage and shipment, then
flattened, cut, shaped, and fastened requires that the coating be
durable. Durability is also required throughout the lifetime of the
metal object, which may be in an outdoor application exposed to
moisture, sunlight, and various chemicals in the atmosphere.
Excellent adhesion of the primer layer, which is a clear or
slightly pigmented resin, is vital to acceptable performance of
coatings over metal during manufacture and throughout the usable
lifetime of the end product.
[0005] In spite of the advantages of using UV light to cure coil
coatings, a major disadvantage with respect to thermal curing is
reduced adhesion of the primer layer to the metal surface. This can
be due to shrinkage of the resin during the rapid cure. Poor
adhesion of the primer layer leads to corrosion and delamination,
which will affect the long term performance of the top coat which
is applied over the primer layer. See for example, G. C. Simmons,
"Studies on the Adhesion of Radiation Cured Coatings to Metal
Substrates." SURCOM Birmingham, Oct. 6-7, 1999, p. 1. and A.
Mejritski, D. C. Neckers, et. al., "Development of Corrosion
Resistant Energy-Curable Coatings." RadTech Report, July/August
2006, p. 13.
[0006] UV cured coil coating primers frequently comprise monomers,
oligomers or resins containing ethylenic unsaturation, such as
acrylates, and adhesion promoters and photoinitiators. The
photoinitiator rapidly undergoes fragmentation during exposure to
the UV light source, initiating polymerization reaction of the
ethylenically unsaturated resin, for example, an acrylate resin. In
order to ensure good adhesion to the metal surface, a sufficient
amount of an adhesion promoting compound, typically a strong acid,
is added to the formulation. The adhesion promoter, which has a
chemical affinity for the metal surface, polymerizes with the resin
and thereby anchors the cured primer layer to the metal
surface.
[0007] CN 1727321 discloses the preparation of ketone derivatives
having multiple hydrophilic groups and their use as
photopolymerization and photocrosslinking catalysts.
[0008] DE 19700064 discloses photocurable thermotropic gels made
from 2-hydroxy acetophenone photoinitiators that are derivatives of
substituted alkylene or polyalkylene oxide containing a hydrophilic
group such as carboxylic acid or hydroxyl.
[0009] JP 2004010534 discloses the reaction of an aromatic
hydroxyketone, which can be substituted by hydroxypolyalkylene
oxide, with a monocarboxylic acid having the maleimide group.
[0010] JP 10087566 discloses 2-butenoic monoester derivatives of
2-hydroxy-2-methylpropan-1-one used as photoinitiators in the
manufacture of hard coatings.
[0011] JP 10017688, JP 09077891, and JP 09328522 describe improving
adhesion and scratch resistance of a coating by grafting monomers
using trialkoxysilyl urethane-substituted propiophenone
photoinitiators.
[0012] US Pub. Appl. No. 2004/204521, incorporated herein in its
entirety by reference, discloses the reaction of nano-scaled
fillers with photoinitiators, such as 2-hydroxy propiophenone
derivatives, functionalized with reactive groups including
trialkoxy silanes, phosphonic acid, and phosphoric acid.
[0013] US Pub. Appl. No. 2002/122872, incorporated herein in its
entirety by reference, discloses a process for coating a surface
using 2-hydroxyacetophenone photoinitiator substituted on the
aromatic ring by either alkylene, or alkylene or polyalkylene oxide
terminated by hydroxyl or carboxylic acid.
[0014] U.S. Pat. No. 5,532,112, incorporated herein in its entirety
by reference, discloses hydroxyl, carboxylic acid and
trialkoxysilyl substituted 2-hydroxyacetophenone photoinitiators
which can form bonds to the cured substrate, e.g., ethylenically
unsaturated systems.
[0015] U.S. Pat. Nos. 4,861,916 and 5,045,573, incorporated herein
in their entirety by reference, disclose carboxylic acid, hydroxyl,
and hydroxyalkylamino substituted 2-hydroxyacetophenone
photoinitiators for the polymerization of ethylenically unsaturated
materials, especially in aqueous media.
[0016] U.S. Pat. No. 6,251,962, incorporated herein in its entirety
by reference, discloses carboxylic and hydroxyl substituted
2-hydroxyacetophenone photoinitiators in high solids paint to
obtain polymers with specific molecular weight and
polydispersity.
[0017] US Pub. Appl. No. 2006/270748, incorporated herein in its
entirety by reference, discloses methylenebis(carbonylphenyl)
compounds containing alpha-hydroxy substituted alkyl groups and a
hydroxyl substituted polyalkylene oxide or hydroxyalkylamino
substituent for use in the cure of coatings and inks.
[0018] U.S. Pat. No. 7,084,183, incorporated herein in its entirety
by reference, discloses difunctional photoinitiator compounds.
[0019] None of the aforementioned patents or publications teaches
the synthesis or use of a compound which combines in the same
compound a photoinitiator with an adhesion promoter for improved
adhesion of a UV cured coating applied over a metal surface.
[0020] The present invention provides a coating formulation
comprising a compound wherein an alpha hydroxy ketone
photoinitiator is chemically bound to an adhesion promoter such as
a carboxylic acid, a phosphonate, or a trialkoxy silane. The
coating adheres strongly to metal surfaces and is effective as a
primer for metals. One embodiment of the invention therefore
provides a UV curable coil coating. In one particular embodiment, a
primer layer for metal surfaces such as a primer used in coil
coating applications is provided. Also provided are novel compounds
comprising an alpha hydroxy ketone photoinitiator chemically bound
to an adhesion promoter such as a carboxylic acid, a phosphonate,
or a trialkoxy silane.
[0021] As the instant photoinitiators are chemically bonded to
organic adhesion promoters, the primer layer formed during cure
will be anchored to the metal surface. One can therefore add less
of a separate adhesion promoter to the formulation, or even not add
any additional adhesion promoter and still ensure that the
polymerized resin is attached to the metal surface.
[0022] Because the instant compounds provide the advantage of
reducing the amount of adhesion promoting compound required to
obtain excellent adhesion, the use of larger concentrations of a
separate adhesion promoting compound, which can adversely affect
the properties of the primer layer and subsequently the topcoat, is
not necessary. Furthermore, because the adhesion promoter anchors
the photoinitiator to the metal surface, the fragments that results
from Norrish type I cleavage of the photoinitiator are less likely
to volatize from the formulation.
[0023] I. V. Khudyakov, T. G. Gantt, M. B. Purvis, and B. J.
Overton, "New developments in UV-Curable Urethane Acrylate
Coatings," in RadTech e/5 2004 Technical Proceedings, describe the
use of oligomers with grafted photoinitiators and adhesion
promoters that give superior properties to acrylate coatings
applied over glass. Besides the different surface, the instant
invention differs from the methodology described by Khudyakov et.
al. in that the instant invention describes the preparation and use
of a photoinitiator which is grafted to an adhesion promoter, but
not to the coating, prior to the curing process. The instant
photoinitiator-adhesion promoter combination is versatile because
it is prepared independently of the oligomers used in the resin and
can therefore be used in a variety of resin systems.
DESCRIPTION OF THE INVENTION
[0024] The present invention provides a coated metal surface which
comprises
[0025] a) a metal substrate, for example steel or aluminum, with at
least one surface which is immediately adjacent to a coating layer
which coating layer comprises
[0026] b) one or more ethylenically unsaturated compounds, for
example, mono- or polyunsaturated monomers, oligomers or
prepolymers, for example acrylate monomers oligomers or
prepolymers, and
[0027] c) from about 0.05 to about 25%, for example from about 0.1
to about 10%, for example from about 1 to about 5% by weight based
on the total weight of the coating layer solids one or more
compounds of the formulae:
##STR00001##
[0028] wherein [0029] G.sub.1 is --H, glycidyl,
--CH.sub.2--CH(OH)--CH--NR.sub.4R.sub.6,
--CH(CH.sub.2OH)--CH--NR.sub.4R.sub.6 or
--CH.sub.2--CH(OH)--CH--NR.sub.4R.sub.6, [0030] G.sub.2 and G.sub.3
are, independently, C.sub.1-C.sub.4 alkyl, or taken together,
pentamethylene,
[0031] R is C.sub.1-C.sub.6 alkylene, C.sub.1-C.sub.6 alkylene-oxy,
C.sub.4-C.sub.6 alkylene interrupted by 1 or 2 oxygen atoms or
C.sub.4-C.sub.6 alkene-oxy interrupted by 1 or 2 oxygen atoms
[0032] A is a group selected from --(O).sub.s--C(.dbd.O)G,
--O--CH.sub.2--C(.dbd.O)G,
--(O).sub.s--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--(O).sub.s--Si(OR.sub.2).sub.2OR.sub.3,
##STR00002##
[0033] s is 0 or 1,
[0034] n is 0, 1 or 2
[0035] L is a direct bond, --CH.sub.2-- or --CH(CH.sub.3)--,
[0036] G is selected from OH,
##STR00003## [0037]
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, [0038]
--R.sub.7--CH.sub.2N(R.sub.8).sub.p--(CH.sub.2).sub.3--Si--(OR.sub.2).sub-
.2OR.sub.3, [0039] --R.sub.10--C(.dbd.O)--OH,
[0040] phenyl or naphthyl, each being substituted by one to three
--COOH, or one or two
--C(.dbd.O)--O--CH2-C(CH.sub.3)(CH.sub.2OH)--COOH and, optionally
by --(C.dbd.O)--O-Z or one or two --COO--R.sub.11 or
--COO--(R.sub.4--O).sub.x--H, where R.sub.4 is not --H, and x is
1-3;
[0041] phenyl or naphthyl, each being substituted by one or two
--(C.dbd.O)--N(R.sub.15).sub.p(R.sub.16).sub.2-p and optionally
substituted by --(C.dbd.O)--O-Z, where p is 0 or 1, R.sub.15 is
--H, C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and R.sub.16 is
C.sub.1-C.sub.4 hydroxyalkyl or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3;
[0042] and
[0043] phenyl substituted at the 2 position by a group C(.dbd.O)OH
and at the 4 or 5 position by a group
##STR00004##
[0044] wherein
[0045] G.sub.4 is a direct bond or --(C.dbd.O)--,
[0046] one of G.sub.7 or G.sub.8 is --H, the other is --H, -Z, or
--R.sub.11,
[0047] R.sub.11 is C.sub.1-C.sub.4 alkyl, C.sub.3-C.sub.4 alkenyl,
or C.sub.3-C.sub.6 alkyl interrupted by 1 or 2 --O--, and
wherein
[0048] R.sub.11 is optionally substituted on a saturated carbon
atom by --OH with the proviso that the substitution does not form
an acetal
[0049] X is [0050] O--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
[0051] --NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
[0052] --N(R.sub.5).sub.p(R.sub.6).sub.2-p, p is 0 or 1,
[0053] Z is
##STR00005##
[0054] Y is --H or --(C.dbd.O)--C(G.sub.1)(G.sub.2)-OG.sub.1,
[0055] R.sub.2 and R.sub.3 are, independently, --H or
C.sub.1-C.sub.4 alkyl, or R.sub.3 is -Z,
[0056] R.sub.4 is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
[0057] R.sub.5 is --H, C.sub.1-C.sub.4 alkyl,
--CH.sub.2--CH(OH)--CH.sub.2--O-Z, --CH(CH.sub.2OH)--CH.sub.2--O-Z,
--CH.sub.2--CH(OZ)-CH.sub.2--OH, or
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3;
[0058] R.sub.6 is C.sub.1-C.sub.4 alkyl substituted by OH or COOH,
or R.sub.6 is --(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
[0059] R.sub.7 is --CH.sub.2-- or --CH(CH.sub.3)--,
[0060] R.sub.8 is --H, C.sub.1-C.sub.4 alkyl,
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3;
[0061] R.sub.9 is --(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3
where R.sub.2 and R.sub.3 are methyl or ethyl,
[0062] R.sub.10 is C.sub.2-C.sub.6 alkylene, alkenylene, or
alkylene substituted by
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, or R.sub.10 is
norbornylene,
[0063] D is AR-- or
##STR00006## [0064]
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
[0065]
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8).sub.p(R.sub.9).sub.2-p,
p is 0 or 1
[0066] --O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH,
[0067] A.sub.1 is --OH, or --NR.sub.12R.sub.13, where R.sub.12 is
--H, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkyl substituted by
--OH or --COOH, or
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.14, where R.sub.14
is --H or C.sub.1-C.sub.4 alkyl, and R.sub.13 is C.sub.1-C.sub.4
alkyl substituted by --OH or --COOH, or R.sub.13 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.14.
[0068] Alkyl is straight or branched chain of the specified number
of carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl,
sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl,
n-decyl, n-undecyl, n-dodecyl.
[0069] Alkylene is a chain of the specified number of carbon atoms
substituted at each terminus as indicated. A branched chain
alkylene may also be present and is a branched carbon chain
substituted at two termini as indicated. Alkylene includes, for
example, methylene, ethylene, propylene, butylene, methylpropylene,
dimethylethylene, hexylene, octylene, 2-ethylhexylene, nonylene,
decylene, undecylene, dodecylene.
[0070] Also provided are new compounds of formula I, II or III
which are very effective as compounds of component c) in the
coatings above. The novel compounds are compounds of formula I, II
or III above wherein
[0071] R is C.sub.1-C.sub.6 alkylene, C.sub.2-C.sub.6 alkylene-oxy,
C.sub.4-C.sub.6 alkylene interrupted by 1 or 2 oxygen atoms, or
C.sub.4-C.sub.6 alkylene-oxy interrupted by 1 or 2 oxygen atoms
[0072] or AR-- taken together is a group --O--CH.sub.2--C(.dbd.O)G,
--O--CH.sub.2--P(.dbd.O)(OR.sub.2)(OR.sub.3),
--O--CH.sub.2--Si(OR.sub.2).sub.2OZ, or
##STR00007##
[0073] With the proviso that in Formula (I)
[0074] A is not --P(.dbd.O)(OH).sub.2 or
--Si(OR.sub.2).sub.2OR.sub.3, unless R.sub.3 is Z;
[0075] and
[0076] also in Formula (I) AR is not
[0077] --O--(CH2).sub.1-6-COOH, --(CH.sub.2).sub.1-6--COOH,
--O--(CH.sub.2).sub.1-6--O--CH.sub.2--COOH,
--(CH.sub.2).sub.1-6--O--CH.sub.2--COOH,
[0078] O--(CH.sub.2).sub.2--O--Si(OR.sub.2).sub.2OR.sub.3, unless
R.sub.3 is Z,
[0079]
O--(CH.sub.2).sub.2--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(O-
R.sub.2).sub.2OR.sub.3, unless R.sub.3 is Z
[0080] --O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH when R is
alkylene-oxy or alkylene-oxy interrupted by oxygen atoms and
R.sub.10 is --CH.sub.2CH.sub.2-, --CH.dbd.CH--, or --CH.dbd.CH--
substituted by once or twice by --CH.sub.3,
[0081] or --O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH when R is
alkylene or alkylene interrupted by oxygen atoms and R.sub.1 and
R.sub.10 combined contain up to 8 saturated carbon atoms;
[0082] in Formula (II)
[0083] when Y is --(C.dbd.O)--C(G.sub.1)(G.sub.2)-OH, D is not
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3
where R.sub.4 is --H or C.sub.1-C.sub.4 alkyl, unless R.sub.3 is
-Z.
[0084] and
[0085] in formula (III)
[0086] A.sub.1 is not --COOH, or --NR.sub.12R.sub.13 where R.sub.12
is --H and R.sub.13 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3, except where
R.sub.3 is -Z.
[0087] For example, novel and effective compounds are compounds of
formula I, II or III above, wherein
[0088] G.sub.1 is H, G.sub.2 and G.sub.3 are each methyl,
[0089] R is C.sub.2-C.sub.6 alkylene or C.sub.2-C.sub.6
alkylene-oxy,
[0090] A is a group selected from --O--C(.dbd.O)G, --C(.dbd.O)G,
--O--(CH.sub.2).sub.2--C(.dbd.O)G,
##STR00008##
[0091] G is selected from [0092]
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.4
is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, [0093]
--R.sub.7--CH.sub.2N(R.sub.8).sub.p--(CH.sub.2).sub.3--Si--(OR.sub.2).sub-
.2OR.sub.3, [0094] R.sub.8is --H, C.sub.1-C.sub.4 alkyl,
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O-Z,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3,
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3; R.sub.7 is
--CH.sub.2-- or --CH(CH.sub.3)--, [0095] --R.sub.10--C(.dbd.O)--OH,
R.sub.10 is C.sub.2-C.sub.6 alkylene, alkenylene, or alkylene
substituted by --(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, or
R.sub.10 is norbornylene,
[0096] phenyl substituted by two --COOH, and, optionally by
--(C.dbd.O)--O-Z;
[0097] phenyl, substituted by
--(C.dbd.O)--N(R.sub.15).sub.p(R.sub.16).sub.2-p and optionally
substituted by --(C.dbd.O)--O-Z, where p is 0 or 1, R.sub.15 is
--H, C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, and R.sub.16 is
C.sub.1-C.sub.4 hydroxyalkyl or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3;
[0098] X is
--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.4
is --H or C.sub.1-C.sub.4 alkyl, or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
--N(R.sub.5).sub.p(R.sub.6).sub.2-p, p is 0 or 1, R.sub.5 is --H,
C.sub.1-C.sub.4 alkyl, --CH.sub.2--CH(OH)--CH.sub.2--O-Z,
--CH(CH.sub.2OH)--CH.sub.2--O-Z, or
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3; R.sub.6 is
C.sub.1-C.sub.4 alkyl substituted by OH or COOH, or R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3;
[0099] and
[0100] in Structure (II),
[0101] when Y is H, D is --(CH.sub.2).sub.1-6COOH,
--O--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
where R.sub.4 is --H or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.2 is methyl
or ethyl, and R.sub.3 is --H, methyl, or ethyl, or
--O--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), wherein
R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH or each of R.sub.5 and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH
[0102] and when Y is --(C.dbd.O)--C(CH.sub.3).sub.2--OH, D is
--O--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6), wherein
R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH or each of R.sub.5 and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH
[0103] and
[0104] In Structure (III), A.sub.1 is --NR.sub.12R.sub.13 where
R.sub.12 and R.sub.13 are each --CH.sub.2CH.sub.2--OH or R.sub.12
is H and R.sub.13 is --CH.sub.2CH.sub.2--OH or
--CH.sub.2CH.sub.2CH.sub.2--OH.
[0105] For example, a compound of the formula
##STR00009## ##STR00010##
[0106] wherein
[0107] A is
--O--CH.sub.2--CH(OH)--CH.sub.2--N(CH.sub.2CH.sub.2OH).sub.2,
--O--C(.dbd.O)--R.sub.10--C(.dbd.O)--OH, R.sub.10 is
--CH.sub.2CH.sub.2-- substituted by either
--(CH.sub.2).sub.3--Si--(OCH.sub.3).sub.3 or
--(CH.sub.2).sub.3--Si--(OCH.sub.2CH.sub.3).sub.3,
[0108] --O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8)(R.sub.9),
R.sub.8 is --CH.sub.2--R.sub.7--(C.dbd.O)--O-Z where R.sub.7 is
--CH.sub.2--, R.sub.9 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where R.sub.2 and
R.sub.3 are methyl or ethyl,
[0109] or A is
--O--(C.dbd.O)--R.sub.7--CH.sub.2N(R.sub.8)(R.sub.9), R.sub.8 is
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.3 or
--CH.sub.2--R.sub.7--(C.dbd.O)--O--CH.sub.2CH.sub.3, where R.sub.7
is --CH.sub.2--, [0110] R.sub.9 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3 where R.sub.2 is
methyl or ethyl and R.sub.3 is -Z,
[0111] D' is
--C(.dbd.O)--NR.sub.4--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3,
where R.sub.4 is --H or
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3, R.sub.2 is methyl
or ethyl, and R.sub.3 is --H, methyl, or ethyl, or [0112]
--CH.sub.2--CH(OH)--CH.sub.2--N(R.sub.5)(R.sub.6),
[0113] R.sub.5 is H and R.sub.6 is
--(CH.sub.2).sub.3--Si--(OR.sub.2).sub.2OR.sub.3or C.sub.2-C.sub.4
alkyl substituted by --OH or each and R.sub.6 is
--(CH.sub.2).sub.3--Si(OR.sub.2).sub.2OR.sub.3 or C.sub.2-C.sub.4
alkyl substituted by --OH:
[0114] for example a compound of the formula
##STR00011##
[0115] wherein R.sub.12 and R.sub.13 are each
--CH.sub.2CH.sub.2--OH or R.sub.12 is H and R.sub.13 is
--CH.sub.2CH.sub.2--OH or --CH.sub.2CH.sub.2CH.sub.2--OH
[0116] or, for example,
[0117] a compound of the formula
##STR00012##
[0118] wherein
[0119] Z is
##STR00013##
[0120] G.sub.2 and G.sub.3 are methyl or taken together,
pentamethylene,
[0121] G.sub.4 is a direct bond or --(C.dbd.O)--,
[0122] and one of G.sub.7 or G.sub.8 is --H, the other is --H or
-Z.
[0123] The photoinitiators of the invention shown above comprise
phenyl rings that are typically ortho- or para-substituted, for
example, the compounds of formula I or II. It should be obvious to
the organic chemist that the synthetic methods known and/or
described herein for preparing such aromatic moieties often
generate meta-substituted materials as minor components. As a
result, in many cases, these minor products will also be present
along with the claimed materials.
[0124] The coating layer of the invention may further comprise
about 1 to about 25, for example about 5 to about 25 weight percent
based on total solids, of an additional photoinitiator or
photoinitiator blend. For example, the additional photoinitiator or
photoinitiator blend comprises one or more compounds selected from
phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide,
2-hydroxy-2-methyl-1-phenyl-1-propanone,
2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpro-
pan-1-one,
2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one,be-
nzophenone and 1-hydroxycyclohexyl phenyl ketone.
[0125] For example, the additional photoinitiator or photoinitiator
blend comprises one or more compounds or blends selected from
[0126] a blend of 20% by weight phenyl
bis(2,4,6-trimethylbenzoyl)phosphine oxide and 80% by weight
2-hydroxy-2-methyl-1-phenyl-1-propanone;
[0127]
2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-met-
hylpropan-1-one;
[0128]
2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one;
[0129] a blend of 50 weight % benzophenone and 50 weight %
1-hydroxycyclohexyl phenyl ketone;
[0130] phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide;
[0131] 1-Hydroxycyclohexyl phenyl ketone;
[0132] and 2-Hydroxy-2-methyl-1-phenyl propan-1-one:
[0133] for example, the additional photoinitiator or photoinitiator
blend comprises the blend 50 weight % benzophenone and 50 weight %
1-hydroxycyclohexyl phenyl ketone or the compound phenyl
bis(2,4,6-trimethylbenzoyl)phosphine oxide.
[0134] The compounds formula I, II or III may be prepared by the
functionalization of photoinitiator molecules using standard
synthetic methodology. Photoinitiator starting materials not
commercially available may be synthesized by Friedel-Crafts
acylation of the appropriate hydrocarbon, followed by bromination
and hydrolysis, according to the methodology of U.S. Pat. No.
5,045,573, incorporated herein in its entirety by reference. In
some cases, it is possible to start with a hydrocarbon that already
contains the attached adhesion promoter, which may be in a
protected form, such as 3,3-diphenylpropionic acid methyl ester,
and subsequently build up the photoinitiator using Friedel-Crafts
chemistry.
[0135] Glycidyl ether derivatives of hydroxyl substituted
photoinitiators, which may be prepared according to the method
described in U.S. Pat. No. 5,532,112 or U.S. Pat. No. 5,837,746,
incorporated herein in their entirety by reference, can be reacted
with an amine substituted by hydroxyalkyl or trialkoxysilylalkyl to
form beta-amino alcohols further substituted by hydroxyl or
trialkoxysilyl groups by adapting the methodology described in
Industrial and Engineering Chemistry, 1956, 48, 94-97. The reaction
of carboxylic acid substituted photoinitiators with commercially
available trialkoxysilylpropyl glycidyl ethers, which is adapted
from the procedure in Industrial and Engineering Chemistry, 1956,
48, 86-93, forms carboxylic acid esters having trialkoxysilyl
substituents
[0136] Trialkoxysilylalkyl amides may be synthesized from the
reaction of commercially available isocyanato substituted
trialkoxysilanes with hydroxyl substituted photoinitiators by using
the methodology described in "A Selective Catalyst for Two
Component Waterborne Polyurethane Coatings," International
Waterborne, High-solids, and Powder coatings Symposium, Feb. 10-12,
1999, New Orleans, La.
[0137] Trialkoxysilyl derivatives may also be synthesized by the
Michael reaction of commercially available trialkoxysilylalkyl
substituted amine with methyl acrylate or methyl methacrylate,
using methodology described in U.S. Pat. No. 4,558,120,
incorporated herein in its entirety by reference, followed by
transesterification with alkoxy substituted photoinitiators.
[0138] Another method to introduce trialkoxysilyl substituents is
the hydrosilation of ethylenically unsaturated derivatives of
photoinitiators, such as those prepared in U.S. Pat. No. 5,532,112
or U.S. Pat. No. 5,837,746, with trialkoxysilanes catalyzed by
rhodium(II) complexes, as described in J. Organometal. Chem., 1981,
208, 401-406.
[0139] The use of trialkoxysilane reagents often results in
exchange reactions with alcohol solvents used in the reactions or
with hydroxyl substituted photoinitiators such as
4'-(2-hydroxyethoxy)-2-hydroxy-2-methylpropiophenone.
[0140] Carboxylic acid derivatives may be formed by reaction of
carboxylic acid anhydrides with hydroxyl substituted
photoinitiators. The reaction may be catalyzed by
4-dimethylaminopyridine as described in J. Org. Chem., 1984, 49,
458-468. The anhydride may be substituted by triethoxysilylalkyl.
Another option is the reaction of hydroxy substituted
photoinitiators with an excess of a di-acyl or tri-acyl substituted
carboxylic acid compound. The reaction may be catalyzed by
pyridine. The unreacted acyl chloride substituents are then
converted to carboxylic acids by hydrolysis.
[0141] The reaction of halogenated photoinitiators with trialkyl
phosphites, as described in Chem. Rev., 1981, 81, 415-430, gives
dialkyl phosphonate derivatives.
[0142] 2-Hydroxy-2-benzoyl substituted cyclohexanecarboxylic acid
derivatives are formed from 6-benzoyl- or substituted
6-benozyl-7-oxa-bicyclo[4.2.0]octan-8-one by hydrolysis or reaction
with an amine substituted by hydroxyl or trialkoxylsilylalkyl.
[0143] The ethylenically unsaturated compounds (b) of the coating
formulation typically contain one or more olefinic double bonds.
They may be low molecular weight (monomeric) or higher molecular
weight (oligomeric), see e.g., U.S. Pat. No. 7,084,183, already
incorporated by reference.
[0144] Examples of monomers having a double bond are alkyl and
hydroxyalkyl acrylates and methacrylates, e.g. methyl, ethyl,
butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl
acrylate, and methyl and ethyl methacrylate. Further examples are
acrylonitrile, acrylamide, methacrylamide,
N-substituted(meth)acrylamides, vinyl esters, such as vinyl
acetate, vinyl ethers, such as isobutyl vinyl ether, styrene,
alkyl- and halo-styrenes, N-vinylpyrrolidone, vinyl chloride and
vinylidene chloride.
[0145] Examples of monomers having a plurality of double bonds are
ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl
glycol diacrylate, hexamethylene glycol diacrylate and bisphenol A
diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane,
trimethylolpropane triacrylate, pentaerythritol triacrylate and
pentaerythritol tetraacrylate, vinyl acrylate, divinylbenzene,
divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl
isocyanurate and tris(2-acryloylethyl)isocyanurate.
[0146] Examples of higher molecular weight (oligomeric)
polyunsaturated compounds are acrylated epoxy resins, acrylated or
vinyl-ether- or epoxy-group-containing polyesters, polyurethanes
and polyethers.
[0147] Further examples of unsaturated oligomers are unsaturated
polyester resins, which are usually produced from maleic acid,
phthalic acid and one or more diols and have molecular weights of
about from 500 to 3000. In addition it is also possible to use
vinyl ether monomers and oligomers, and also maleate-terminated
oligomers having polyester, polyurethane, polyether, polyvinyl
ether and epoxide main chains. Combinations of
vinyl-ether-group-carrying oligomers and polymers, as described in
U.S. Pat. No. 5,334,455, incorporated herein by reference, are
especially suitable, but copolymers of monomers functionalised with
vinyl ether and maleic acid also come into consideration.
[0148] Also suitable are compounds having one or more
free-radical-polymerisable double bonds. The
free-radical-polymerisable double bonds in such compounds are
preferably in the form of (meth)acryloyl groups. Here and in the
following, (meth)acryloyl and (meth)acrylic mean acryloyl and/or
methacryloyl, and acrylic and/or methacrylic, respectively. At
least two polymerisable double bonds in the form of (meth)acryloyl
groups are preferably contained in the molecule. The compounds in
question may be, for example, (meth)acryloyl-functional oligomeric
and/or polymeric compounds of poly(meth)acrylate. The
number-average molar mass of that compound may be, for example,
from 300 to 10 000, preferably from 800 to 10 000, The compounds
preferably containing free-radical-polymerisable double bonds in
the form of (meth)acryloyl groups can be obtained by customary
methods, for example by reaction of poly(meth)acrylates with
(meth)acrylic acid. These and further preparation methods are
described in the literature and known to the person skilled in the
art.
[0149] Such unsaturated oligomers can also be termed
prepolymers.
[0150] It is also possible to use in component (b) unsaturated
acrylates having reactive functional groups. The reactive
functional group may be selected, for example, from a hydroxy,
thiol, isocyanate, epoxide, anhydride, carboxy, amino and blocked
amino group. Examples of unsaturated acrylates containing OH groups
are hydroxyethyl acrylates, hydroxybutyl acrylates and also
glycidyl acrylates.
[0151] Examples of suitable monomers which are typically used to
form the backbone (the base polymer) of such functionalised
acrylate and methacrylate polymers are, for example, acrylate,
methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl
methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl
acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, etc. In addition, suitable amounts of
functional monomers are copolymerised during the polymerisation in
order thus to obtain the functional polymers. Acid-functionalised
acrylate or methacrylate polymers are obtained with the aid of
acid-functional monomers such as acrylic acid and methacrylic acid.
Hydroxy-functional acrylate or methacrylate polymers are obtained
from hydroxy-functional monomers, such as 2-hydroxyethyl
methacrylate, 2-hydroxypropyl methacrylate, 3,4-dihydroxybutyl
methacrylate, or from acrylates which are derived from glycerol
derivatives. Epoxy-functionalised acrylate or methacrylate polymers
are obtained with the aid of epoxy-functional monomers such as
glycidyl methacrylate, 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl
methacrylate, 2,3-epoxycyclohexyl methacrylate, 10,11-epoxyundecyl
methacrylate, etc. Likewise, isocyanate-functionalised polymers,
for example, can be produced from isocyanate-functionalised
monomers, for example
meta-isopropenyl-.alpha.,.alpha.-dimethylbenzyl isocyanate.
Amino-functionalised polymers are, for example, polyacrylamides,
and nitrile-group-containing polymers are, for example,
polyacrylonitriles.
[0152] For example, typical of such compounds are ethylenically
unsaturated mono- or polyfunctional carboxylic acids and polyols or
polyepoxides, and polymers having ethylenically unsaturated groups
in the chain or in side groups, e.g. unsaturated polyesters,
polyamides and polyurethanes and copolymers thereof, alkyd resins,
polybutadiene and butadiene copolymers, polyisoprene and isoprene
copolymers, polymers and copolymers having (meth)acrylic groups in
side chains, and also mixtures of one or more such polymers.
[0153] Examples of suitable mono- or poly-functional unsaturated
carboxylic acids are acrylic acid, methacrylic acid, crotonic acid,
itaconic acid, cinnamic acid, maleic acid, fumaric acid, itaconic
acid, and unsaturated fatty acids such as linolenic acid and oleic
acid. Acrylic and methacrylic acid are preferred.
[0154] It is also possible to use saturated di- or poly-carboxylic
acids in admixture with unsaturated carboxylic acids. Examples of
suitable saturated di- or poly-carboxylic acids include, for
example, tetrachlorophthalic acid, tetrabromophthalic acid,
phthalic anhydride, adipic acid, tetrahydrophthalic acid,
isophthalic acid, terepthalic acid, trimellitic acid,
heptanedicarboxylic acid, sebacic acid, dodecanedicarboxylic acid,
hexahydrophthalic acid, etc.
[0155] Suitable polyols include aromatic and, especially, aliphatic
and cycloaliphatic polyols. Examples of aromatic polyols are
hydroquinone, 4,4'-dihydroxydiphenyl,
2,2-di(4-hydroxyphenyl)propane, and novolaks and resols. Examples
of polyepoxides are those based on the said polyols, especially the
aromatic polyols and epichlorohydrin. Also suitable as polyols are
polymers and copolymers that contain hydroxyl groups in the polymer
chain or in side groups, e.g. polyvinyl alcohol and copolymers
thereof or polymethacrylic acid hydroxyalkyl esters or copolymers
thereof. Further suitable polyols are oligoesters having hydroxyl
terminal groups.
[0156] Examples of aliphatic and cycloaliphatic polyols include
alkylenediols having, for example, from 2 to 12 carbon atoms, such
as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or
1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol,
diethylene glycol, triethylene glycol, polyethylene glycols having
molecular weights of preferably from 200 to 1500,
1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,
1,4-dihydroxymethylcyclohexane, glycerol,
tris(.beta.-hydroxyethyl)amine, trimethylolethane,
trimethylolpropane, pentaerythritol, dipentaerythritol and
sorbitol.
[0157] The polyols may be partially or fully esterified by one or
by different unsaturated carboxylic acid(s), it being possible for
the free hydroxyl groups in partial esters to be modified, for
example etherified, or esterified by other carboxylic acids.
[0158] Specific examples of esters useful in component (b) include
trimethylolpropane triacrylate, trimethylolethane triacrylate,
trimethylolpropane trimethacrylate, trimethylolethane
trimethacrylate, tetramethylene glycol dimethacrylate, triethylene
glycol dimethacrylate, tetraethylene glycol diacrylate,
pentaerythritol diacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
dipentaerythritol triacrylate, dipentaerythritol tetraacrylate,
dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
tripentaerythritol octaacrylate, pentaerythritol dimethacrylate,
pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate,
dipentaerythritol tetramethacrylate, tripentaerythritol
octamethacrylate, pentaerythritol diitaconate, dipentaerythritol
trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol
hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol
diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol
diitaconate, sorbitol triacrylate, sorbitol tetraacrylate,
pentaerythritol-modified triacrylate, sorbitol tetramethacrylate,
sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates
and methacrylates, glycerol di- and tri-acrylate, 1,4-cyclohexane
diacrylate, bisacrylates and bismethacrylates of polyethylene
glycol having a molecular weight of from 200 to 1500, and mixtures
thereof.
[0159] The following esters are also suitable: dipropylene glycol
diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol
diacrylate, glycerol ethoxylate triacrylate, glycerol propoxylate
triacrylate, trimethylolpropane ethoxylate triacrylate,
trimethylolpropane propoxylate triacrylate, pentaerythritol
ethoxylate tetraacrylate, pentaerythritol propoxylate triacrylate,
pentaerythritol propoxylate tetraacrylate, neopentyl glycol
ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate.
[0160] Also suitable as component (b) are the amides of identical
or different unsaturated carboxylic acids and aromatic,
cycloaliphatic and aliphatic polyamines having preferably from 2 to
6, especially from 2 to 4, amino groups. Examples of such
polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-,
1,3- or 1,4-butylenediamine, 1,5-pentylenediamine,
1,6-hexylenediamine, octylenediamine, dodecylenediamine,
1,4-diaminocyclohexane, isophoronediamine, phenylenediamine,
bisphenylenediamine, di-.beta.-aminoethyl ether,
diethylenetriamine, triethylenetetramine and
di(.beta.-aminoethoxy)- and di(.beta.-aminopropoxy)-ethane. Further
suitable polyamines are polymers and copolymers which may have
additional amino groups in the side chain and oligoamides having
amino terminal groups. Examples of such unsaturated amides are:
methylene bisacrylamide, 1,6-hexamethylene bisacrylamide,
diethylenetriamine trismethacrylamide,
bis(methacrylamidopropoxy)ethane, .beta.-methacrylamidoethyl
methacrylate and N-[(.beta.-hydroxyethoxy)ethyl]-acrylamide.
[0161] Suitable unsaturated polyesters and polyamides are derived,
for example, from maleic acid and diols or diamines. The maleic
acid may have been partially replaced by other dicarboxylic acids.
They may be used together with ethylenically unsaturated
comonomers, e.g. styrene. The polyesters and polyamides may also be
derived from dicarboxylic acids and ethylenically unsaturated diols
or diamines, especially from those having longer chains of e.g.
from 6 to 20 carbon atoms. Examples of polyurethanes are those
composed of saturated diisocyanates and unsaturated diols or
unsaturated diisocyanates and saturated diols.
[0162] Aminoacrylates are also suitable for use in component (b).
For example acrylates which have been modified by reaction with
primary or secondary amines, as described, for example, in U.S.
Pat. No. 3,844,916; U.S. Pat. No. 5,482,649; U.S. Pat. No.
5,734,002, each incorporated herein by reference, and EP 280 222.
Such amine-modified acrylates are also termed aminoacrylates. Many
suitable aminoacrylates are commercially available.
[0163] The photopolymerisable compounds (b) can be used alone or in
any desired mixtures.
[0164] The photoinitiators of the instant invention are suitable
quite generally as photoinitiators in a wide variety of systems in
addition to coil coatings and metal primers, in particular, those
systems comprising ethylenically unsaturated compounds. Such
systems include, for example, overprint coatings, printing inks,
systems used in the manufacture of electronic printed circuit
boards and printing plates, and in the coating of various other
substrates, such as wood, plastics, paper and glass
[0165] The invention accordingly relates also to a composition
comprising (b) at least one ethylenically unsaturated compound, for
example, an acrylate or amino acrylate, (c) a photoinitiator of
formula I, II or III, in particular the compounds identified as
novel above, (d) optionally, further photoinitiators and co
initiators (e) optionally a film-forming binder based on a
thermoplastic or thermocurable resin; (f) optionally, further
additives. Of course, each of the optional components (d), (e) and
(f) may also be part of the coated metal surface of the instant
invention.
[0166] Component (e) is, for example, generally a film-forming
binder based on a thermoplastic or thermocurable resin,
predominantly on a thermocurable resin. Examples thereof are alkyd,
acrylic, polyester, phenol, melamine, epoxy and polyurethane resins
and mixtures thereof. Examples thereof are described, for example,
in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol.
A18, pp. 368 426, VCH, Weinheim 1991.
[0167] Component (e) may be a cold-curable or hot-curable binder,
with the addition of a curing catalyst possibly being advantageous.
Suitable catalysts that accelerate the full cure of the binder are
described, for example, in Ullmann's Encyclopedia of Industrial
Chemistry, Vol. A18, page 469, VCH Verlagsgesellschaft, Weinheim
1991.
[0168] Examples of particular binders suitable as component (e)
are: 1. surface-coating compositions based on cold- or
hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine
resins or mixtures of such resins, optionally with the addition of
a curing catalyst; 2. two-component polyurethane surface-coating
compositions based on hydroxyl-group-containing acrylate, polyester
or polyether resins and aliphatic or aromatic isocyanates,
isocyanurates or polyisocyanates; 3. two-component polyurethane
surface-coating compositions based on thiol-group-containing
acrylate, polyester or polyether resins and aliphatic or aromatic
isocyanates, isocyanurates or polyisocyanates; 4. single-component
polyurethane surface-coating compositions based on blocked
isocyanates, isocyanurates or polyisocyanates, which are unblocked
during stoving; the addition of melamine resins is also possible;
5. single-component polyurethane surface-coating compositions based
on aliphatic or aromatic urethanes or polyurethanes and
hydroxyl-group-containing acrylate, polyester or polyether resins;
6. single-component polyurethane surface-coating compositions based
on aliphatic or aromatic urethane acrylates or polyurethane
acrylates having free amine groups in the urethane structure, and
melamine resins or polyether resins, optionally with the addition
of a curing catalyst; 7. two-component surface-coating compositions
based on (poly)ketimines and aliphatic or aromatic isocyanates,
isocyanurates or polyisocyanates; 8. two-component surface-coating
compositions based on (poly)ketimines and an unsaturated acrylate
resin or a polyacetoacetate resin or a methacrylamidoglycolate
methyl ester; 9. two-component surface-coating compositions based
on carboxyl- or amino-group-containing polyacrylates and
polyepoxides; 10. two-component surface-coating compositions based
on anhydride-group-containing acrylate resins and a polyhydroxy or
polyamino component; 11. two-component surface-coating compositions
based on acrylate-containing anhydrides, and polyepoxides; 12.
two-component surface-coating compositions based on
(poly)oxazolines and anhydride-group-containing acrylate resins, or
unsaturated acrylate resins or aliphatic or aromatic isocyanates,
isocyanurates or polyisocyanates; 13. two-component surface-coating
compositions based on unsaturated (poly)acrylates and
(poly)malonates; 14. thermoplastic polyacrylate surface-coating
compositions based on thermoplastic acrylate resins or
extrinsically crosslinking acrylate resins, in combination with
etherified melamine resins; 15. surface-coating composition
systems, especially clear surface-coating compositions, based on
malonate-blocked isocyanates with melamine resins (e.g.
hexamethoxymethylG16 melamine) as crosslinker (acid-catalysed); 16.
UV-curable systems based on oligomeric urethane acrylates and/or
acylate acrylates, optionally with the addition of other oligomers
or monomers; 17. dual-cure systems, which are first cured thermally
and then UV-cured, or vice versa, constituents of the
surface-coating composition containing double bonds which can be
made to react by UV light and photoinitiators and/or by
electron-beam curing.
[0169] In addition to the photoinitiator, the photopolymerisable
mixtures may optionally comprise further conventional additives
(f), depending on the intended use.
[0170] Examples thereof are: antioxidants, optical brighteners,
fillers, thermal inhibitors which are intended to prevent premature
polymerisation, antistats, wetting agents or flow improvers,
further adhesion enhancers; thermal drying or curing catalysts, for
example organometallic compounds, amines or/and phosphines; UV
absorbers and light stabilizers, for example those from the group
of the 2-(2'-hydroxyphenyl)-benzotriazoles, of the
2-hydroxybenzophenones, esters of unsubstituted or substituted
benzoic acids, acrylates, sterically hindered amines, oxalic acid
diamides, 2-(2-hydroxy-phenyl)-1,3,5-triazines, phosphites and
phosphonites. Such compounds are common in the art and are also
described in Published US appl. No. 20060270748, incorporated
herein in its entirety by reference.
[0171] Photopolymerisation can also be accelerated by addition, as
further additives (f), of photosensitisers that shift or broaden
the spectral sensitivity. These include especially aromatic
carbonyl compounds, for example benzophenone, thioxanthone,
including especially isopropylthioxanthone, anthraquinone and
3-acylcoumarin derivatives, terphenyls, styryl ketones, and
3-(aroylmethylene)-thiazolines, camphorquinone and also eosin,
rhodamine and erythrosine dyes.
[0172] The formulations may also comprise dyes and/or white or
coloured pigments. Depending on the intended use, both inorganic
and organic pigments may be used.
[0173] The additives (f) described above are conventional in the
art and accordingly are used in the amounts customary in the
art.
[0174] It is also possible to add solvents or water to the coating
compositions herein. Suitable solvents are solvents which are known
to the person skilled in the art and are conventional especially in
coating technology. Radiation-curable aqueous prepolymer
dispersions are obtainable commercially in many variations. They
are to be understood as being a dispersion of water and at least
one prepolymer dispersed therein.
[0175] The coating composition, for example, the coating layer of
the coated metal surface may be a powder coating. The powder
coatings may be based on solid resins and monomers containing
reactive double bonds (compounds (b)), for example maleates, vinyl
ethers, acrylates, acrylamides and mixtures thereof. The powder
coatings may also comprise binders, as are described, for example,
in U.S. Pat. No. 5,620,751, incorporated herein in its entirety by
reference, and EP 636 669. The UV-curable powder coatings may also
comprise white or coloured pigments.
[0176] It is also possible that the coating layer is a "dual cure"
coating formulation using the photoinitiators according to the
invention. Such formulations are known to the person skilled in the
art and are both thermally cured and UV-cured. Such formulations
can be found, for example, in U.S. Pat. No. 5,922,473, incorporated
herein in its entirety by reference.
[0177] Frequently, the coating layer comprising components (b) and
(c), and any additional optional components, is in the form of a
dispersion. Dispersants useful in such an application are well
known in the art, e.g., U.S. Pat. No. 7,084,183, incorporated
herein in its entirety by reference.
[0178] A substrate, for example, a metal substrate, can be coated
by applying a liquid composition, i.e., a solution or a suspension
comprising components (b) and (c), plus any optional components, to
the substrate. The choice of solvent and its concentration are
governed chiefly by the nature of the composition and the coating
method. The solvent is frequently inert, that is to say it does not
enter into any chemical reaction with the components, although
reactive diluents are known and may be used, and it should be
capable of being removed again on drying after the coating
operation. Suitable inert solvents include, for example, ketones,
ethers and esters, such as methyl ethyl ketone, isobutyl methyl
ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone,
dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol,
1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl
acetate and ethyl 3-ethoxypropionate.
[0179] The coating formulation is applied uniformly to a substrate
by means of known coating methods, for example by spin-coating,
immersion, knife coating, curtain pouring, brush application or
spraying, especially by electrostatic spraying and reverse-roll
coating, and also by electrophoretic deposition. It is also
possible to apply the photosensitive layer to a temporary flexible
support and then coat the final substrate by transferring the layer
via lamination. Examples of types of application are to be found,
for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th
Edition, Vol. A18, pp. 491 500.
[0180] The amount applied (layer thickness) and the nature of the
substrate (layer support) are dependent on the desired field of
application. The range of dry layer thicknesses generally includes
values from about 0.1 micron to more than about 100 microns.
[0181] The photosensitivity of the compositions according to the
invention usually extends from approximately 200 nm to within the
IR range, often UV light, about 200 nm to about 400 nm is very
effective. Generally, light from about 200 nm to about 450 nm can
be employed with excellent success. Suitable radiation is present,
for example, in sunlight or light from artificial light sources.
Accordingly a large number of the most varied kinds of light source
may be used. Both point sources and planiform radiators (lamp
carpets) are suitable. Examples are: carbon arc lamps, xenon arc
lamps, medium-pressure, high-pressure and low-pressure mercury
radiators, doped, where appropriate, with metal halides (metal
halide lamps), microwave-excited metal vapour lamps, excimer lamps,
superactinic fluorescent tubes, fluorescent lamps, argon
incandescent lamps, flash lamps, e.g. high-energy flash lamps,
photographic floodlight lamps, light-emitting diodes (LED),
electron beams and X-rays. The distance between the lamp and the
substrate to be exposed may vary according to the intended use and
the type and strength of the lamp and may be, for example, from 2
cm to 150 cm. Laser light sources are suitable, for example excimer
lasers, such as Krypton-F lasers for exposure at 248 nm. Lasers in
the visible range may also be used.
[0182] As already mentioned, curing in the process according to the
invention can be carried out simply by irradiation with
electromagnetic radiation. Depending on the composition of the
formulation to be cured, however, thermal curing before, during or
after the irradiation is advantageous.
[0183] Thermal curing is carried out by methods known to the person
skilled in the art. In general, the curing is carried out in an
oven, e.g. a circulating air oven, on a hot plate or by irradiation
with IR lamps. Unassisted curing at room temperature is also
possible, depending on the binder system used. The curing
temperatures are generally between room temperature and 150.degree.
C., for example from 25 to 150.degree. C., or from 50 to
150.degree. C. In the case of powder coatings or coil coatings, the
curing temperatures may be even higher, e.g. up to 350.degree.
C.
[0184] One particular embodiment of the invention is a formulation
useful as a primer coil coating which comprises a compound wherein
an alpha hydroxy ketone photoinitiator moiety is chemically bound
to an adhesion promoter such as a carboxylic acid, a phosphonate,
or a trialkoxy silane. The coating formulation of the invention can
of course be overcoating with one or more additional coating
layers.
[0185] Measurement of physical properties of a UV cured primer over
metal showed good to excellent adhesion of the primer layer
obtained using the instant photoinitiators that are chemically
bound to adhesion promoters. The instant photoinitiators, in some
cases, gave primer layers with better adhesion properties than did
photoinitiators that were not chemically modified with adhesion
promoters.
EXAMPLES
Example 1A
2-Hydroxy-2-methyl-1-[4-(2-oxiranylmethoxyethoxy)phenyl]propan-1-one
##STR00014##
[0187] Epichlorohydrin (24 g, 0.261 mol) is added to a mixture of
16.31 g (0.408 mol) of sodium hydroxide, 45 ml of water, and 0.761
g (2.24 mmol) of tetrabutylammonium hydrogen sulfate that is
previously cooled in an ice-water bath for 20 minutes. To this
mixture is added dropwise over 45 minutes with rapid stirring, a
solution of 10.32 g (46.0 mmol) of
2-hydroxy-1-[4-(2-hydroxy-ethoxy)phenyl]-2-methylpropan-1-one in 95
ml of 1,2-dimethoxyethane. The reaction mixture is stirred
overnight at room temperature. The aqueous layer is removed, and
the organic layer is concentrated. Purification by flash
chromatography on silica gel (1:1 heptane:ethyl acetate) affords
9.20 g (71% of theoretical yield) of the title compound, a pale
yellow liquid.
Example 1B
Mixture of
2-Hydroxy-1-(4-{2-[2-hydroxy-3-(3-triethoxysilylpropylamino)pro-
poxy]ethoxy}-phenyl)-2-methylpropan-1-one and
2-Hydroxy-1-[4-(2-{2-hydroxy-3-[(2-hydroxy-3-{2-[4-(2-hydroxy-2-methylprop-
ionyl)phenoxy]ethoxy}propyl)-(3-triethoxysilylpropyl)amino]-propoxy}ethoxy-
)phenyl]-2-methylpropan-1-one
##STR00015##
[0189] To a mixture of 5.09 g (23 mmol) of
3-aminopropyltriethoxysilane, 30 ml of 1,2-dimethoxyethane and 30
ml of 2-propanol is added 8.99 g (32.1 mmol) of the compound
prepared in Example 1A. The reaction mixture is heated at a gentle
reflux for 23 hours. Solvent is evaporated to afford 14.37 g of a
pale yellow oil corresponding to a mixture of the title
compounds.
Example 2
1-[4-(2-{3-[Bis(2-hydroxyethyl)amino]-2-hydroxypropoxyethoxy}phenyl]-2-hyd-
roxy-2-methylpropan-1-one
##STR00016##
[0191] To a mixture of 3.23 g (30.7 mmol) of diethanolamine in 32
ml of 2-propanol is added a solution of 9.01 g (32.1 mmol) of the
compound of Example 1A in 20 ml of 1,2-dimethoxyethane. The mixture
is heated at reflux for 4 hours. An additional portion of
diethanolamine (0.47 g, 4.47 mmol) is added to the reaction
mixture, and the reaction is heated at reflux for 5 hours. Solvent
is evaporated to obtain 13.37 g of the title compound, a yellow
oil.
Example 3
Mixture of
2-Hydroxy-1-(4-{2-[2-hydroxy-3-(3-hydroxypropylamino)propoxy]et-
hoxy}-phenyl)-2-methylpropan-1-one and
2-Hydroxy-1-[4-(2-{2-hydroxy-3-[(2-hydroxy-3-{2-[4-(2-hydroxy-2-methylprop-
ionyl)-phenoxy]ethoxy}propyl)-(3-hydroxypropyl)amino]-propoxy}ethoxy)pheny-
l]-2-methylpropan-1-one
##STR00017##
[0193] To a mixture of 2.22 g (29.6 mmol) of 3-amino-1-propanol in
20 ml of 1,2-dimethoxyethane and 40 ml of 2-propanol is added a
solution of 11.57 g (41.3 mmol) of the compound of Example 1A in 20
ml of 1,2-dimethoxyethane. The mixture is heated at reflux
overnight. Solvent is evaporated to afford a mixture of the title
compounds.
Example 4
[4-(2-Hydroxy-2-methylpropionyl)phenoxy]acetic acid
##STR00018##
[0195] A chilled mixture (0.degree. C.) of acetonitrile (200 ml)
and water (300 ml) is added drop wise to a chilled mixture of 15.0
g (66.9 mmol) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one, 2.00 g
(9.38 mmol) of 1-oxyl-4-acetamido-2,2,6,6-tetramethylpiperidine,
4.00 g (12.4 mmol) of iodobenzene diacetate, and 5.0 g (59.5 mmol)
of sodium bicarbonate. The reaction mixture is stirred 15 minutes
at 0.degree. C., and 5.1 g (61 mmol) of sodium bicarbonate is
added. The reaction mixture is stirred for 2 hours at 0.degree. C.
The reaction is warmed to room temperature, and stirred for 90
minutes. The reaction mixture is made basic by the addition of
sodium hydroxide, and then filtered. The filtrate is acidified and
extracted with chloroform. The organic layer is concentrated to
give 20 g of crude yellow oil that is crystallized to give 11 grams
(69% yield) of the title compound, a tan solid.
Example 5
1-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}hydrogen
2-(3-triethoxysillylpropyl)succinate
1-{3-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}hydrogen
2-(3-triethoxysillylpropyl)succinate
##STR00019##
[0197] 2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one
(4.5g, 20.1 mmol), pyridine (2.13 g) and 1,2-dimethoxyethane (30
ml) are mixed together. After solids dissolve,
3-(triethoxysilyl)propylsuccinic anhydride (6.14 g, 20.2 mmol) is
added and the mixture is allowed to stand at room temperature for
one hour. The reaction mixture is then heated at 50.degree. C. for
5 hours (oil bath). The mixture is cooled slowly and stirred
overnight (16 hours) at room temperature.
[0198] The reaction solution is divided into two equal parts.
Solvent is evaporated from one part to give 5.36 g of light brown
viscous oil, which is a mixture of the title compounds.
[0199] The other half of the crude product mixture is stirred
overnight with 8.3 g of Dowex 50W-2 100-200 mesh ion-exchange
resin. The resin is removed by filtration, and solvent is
evaporated to give 5.87 g of light brown oil, which is a mixture of
the title compounds.
Example 6
3,3'-Bis[{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxy}carbonyl]benzop-
henone-4,4'-dicarboxylic acid
3,4'-Bis[{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxy}carbonyl]benzop-
henone-4,4'-dicarboxylic acid
4,4'-Bis[{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxy}carbonyl]benzop-
henone-4,4'-dicarboxylic acid
##STR00020##
[0201] The reaction product, a mixture of isomers, is obtained by
stirring 8.96 g (40.0 mmol) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one, 6.64 g
(20.6 mmol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride
and 1.75 g (22.1 mmol) of pyridine in 60 ml of tetrahydrofuran at
70.degree. C. until the reaction is complete. Solvent is evaporated
to obtain 14.56 g of light brown oil.
Example 7
4-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}hydrogen
(Z)-2-Methylbut-2-enedioate
1-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}hydrogen
(Z)-2-Methylbut-2-enedioate
##STR00021##
[0203] To a mixture of 6.72 g (0.0300 mol) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one and
3.49 g (0.0311 mol) of citraconic anhydride, dissolved in 50 ml of
tetrahydrofuran, is added, at room temperature, 3 drops of
pyridine. The reaction mixture is heated at 60.degree. C. for 16
hours. Solvent is evaporated to give 10.24 g of an oil, which is a
mixture of the title compounds.
Example 8
1-(2-Carboxy-3-hydroxy-2-methylpropyl)3,5-bis-{2-[4-(2-hydroxy-2-methylpro-
pionyl)phenoxy]ethyl}benzene-1,3,5-tricarboxylate
##STR00022##
[0205] A mixture of 6.72 g (30.0 mmol) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one and 50
ml of 1,2-dimethoxyethane is heated to 50.degree. C.
1,3,5-Benzenetricarboxylic acid chloride (5.31 g, 20.0 mmol) is
added, followed by 3.10 g (39.2 mmol) of pyridine. The mixture
becomes cloudy. The reaction mixture is stirred overnight at
40.degree. C., and the temperature is raised to 70.degree. C. After
4 hours, 2,2-bis(hydroxymethyl)propionic acid (2.50 g, 18.6 mmol)
is added to the reaction mixture, followed by 3.25 g (41.1 mmol) of
pyridine. The reaction mixture is stirred overnight at 70.degree.
C. The reaction mixture is filtered and concentrated to obtain a
light brown syrup which contains the title compound.
Example 9
2,4-Bis[{2-[4-(2-hydroxy-2-methyl-propionyl)phenoxy]ethoxy}carbonyl]benzen-
e-1,5-dicarboxylic acid
1,4-Bis[{2-[4-(2-hydroxy-2-methyl-propionyl)phenoxy]ethoxy}carbonyl]benzen-
e-1,5-dicarboxylic acid
##STR00023##
[0207] The reaction product mixture is obtained from
benzene-1,2,4,5-tetracarboxylic anhydride,
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one and
pyridine according to the procedure of Example 6.
Example 10
3,3'-Bis-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxycarbonyl}bipheny-
l-4,4'-dicarboxylic acid
3,4'-Bis-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxycarbonyl}bipheny-
l-4,4'-dicarboxylic acid
##STR00024##
[0209] To 3,3'4,4'-biphenyltetracarboxylic dianhydride (3.00 g,
13.4 mmol) and
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one (4.49
g, 20.0 mmol) are added 40 ml dried, commercial tetrahydrofuran and
pyridine (1.15 g, 14.5 mmol). The mixture is stirred at 70.degree.
C. until the reaction is complete. Most of the solvent is
evaporated to give 11.0 g (contains solvent) of colorless, clear,
viscous oily product, which is a mixture of isomers.
Example 11
Bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]methyl(3-triethoxysilylpropyl)c-
arbamate
##STR00025##
[0211] A solution of 87.9 g (0.24 mol) of
bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]methanol in
1,2-dimethoxyethane is added to a mixture of 49.5 g (0.20 mol) of
3-triethoxysilylpropyl isocyanate and 0.097 g (0.20 mmol) of
zirconium(IV) acetylacetonate. The reaction mixture is stirred at
60.degree. until the reaction is complete. Solvent is evaporated to
give the title compound.
Example 12
2-{3-[Bis-(2-hydroxyethyl)amino]-2-hydroxy-propoxy}-1-[4-(2-{3-[bis-(2-hyd-
roxyethyl)amino]-2-hydroxy-propoxy}ethoxy)phenyl]-2-methylpropan-1-one
##STR00026##
[0213] The reaction time in Example 1A is extended. The aqueous
layer is removed, and the organic layer is concentrated.
Purification by flash chromatography on silica gel (1:1
heptane:ethyl acetate) affords
2-methyl-2-oxiranylmethoxy-1-[4-(2-oxiranylmethoxy-ethoxy)-phenyl]-propan-
-1-one. This compound is dissolved in 1,2-dimethoxyethane and the
solution is added to a mixture of 1.8 equivalents of diethanolamine
and isopropyl alcohol. The reaction mixture is heated overnight at
reflux temperature. Solvent is evaporated to give a mixture of the
title compound and the product of Example 2.
Example 13
3-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxycarbonyl}benzophenone-3-
',4,4'-tricarboxylic acid
4-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxycarbonyl}benzophenone-3-
',4,4'-tricarboxylic acid
##STR00027##
[0215] The reaction product, a mixture of isomers, is obtained by
stirring 4.48 g (20.0 mmol) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one, 6.44 g
(20.0 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and
60 ml of 1,2-dimethoxyethane at 85.degree. C. overnight. Solvent is
evaporated to give 15.29 g of a semi-solid. Analysis (MS) shows the
majority of the material is consistent with the title compounds.
The product also contains the product of Example 6.
Example 14
1-{2-[4-(2-hydroxy-2-methyl-propionyl)phenethyl}hydrogen2-(3-triethoxysill-
ylpropyl)succinate
4-{2-[4-(2-hydroxy-2-methyl-propionyl)phenethyl}hydrogen
2-(3-triethoxysillylpropyl)succinate
##STR00028##
[0217] 3-(Triethoxysilyl)propylsuccinic anhydride (6.32 g, 20.8
mmol) is added drop wise at room temperature to a mixture of 4.24 g
(20.4 mmol) of
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl-2-methylpropan-1-one (see
Example 15), 1.65 g (20.9 mmol) of pyridine, and 30 ml of
1,2-dimethoxyethane. The reaction mixture is stirred at room
temperature for 30 minutes, then at 50.degree. C. until the
reaction is complete. Most of the solvent is evaporated to obtain
14.06 g of an oil, which is a mixture of the title compounds.
Example 15
3,3'-Bis[{2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethoxy}carbonyl]benzoph-
enone-4,4'-dicarboxylic acid
3,4'-Bis[{2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethoxy}carbonyl]benzoph-
enone-4,4'-dicarboxylic acid
##STR00029##
[0219] Isobutyryl chloride (114 g, 1.07 mol) is added drop wise at
-5 to 0.degree. C. over 40 minutes to 295 g (2.21 mol) of anhydrous
aluminum chloride in 160 ml of methylene chloride. Stirring is
continued for 30 min, and 2-phenylethyl acetate (164.2 g, 1.00 mol)
is then added drop wise at -5 to 0.degree. C. over 2 hours. The
mixture is stirred an additional 4 hours at -5 to 0.degree. C., and
then poured into a mixture of concentrated hydrochloric acid and
ice. The organic layer is washed with water, dried and concentrated
to give 190.5 g of crude 2-(4-isobutyrylphenyl)ethyl acetate, a
colorless liquid.
[0220] A 110 g portion of crude 2-(4-isobutyrylphenyl)ethyl acetate
is dissolved in 100 ml of glacial acetic acid. Bromine (93.64 g,
0.59 mol) is added over one hour at 25.degree. C. The mixture is
stirred overnight at room temperature, and then poured into 1500 ml
of water. The product is extracted with ethyl acetate. The combined
extracts are dried and concentrated to give 160.11 g of
2-[4-(2-bromo-2-methyl-propionyl)phenyl]acetate, a viscous oil,
which is dissolved in 200 ml of ethanol. A 32% sodium hydroxide
solution is added over 20 minutes. The mixture is stirred until
hydrolysis is complete, and ethanol is evaporated. The oily residue
is poured into ice water, and this mixture is extracted with ethyl
acetate. The organic layer is dried, filtered, and concentrated.
One-half of the crude product is recrystallized from a mixture of
acetone and petroleum ether to give 12.78 g of
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, a
white crystalline solid.
[0221] Pyridine (2.43 g, 30.7 mmol) is added to a mixture of 6.24 g
(30.0 mmol) of
1-[4-(2-hydroxyethyl)phenyl]-2-hydroxy-2-methylpropan-1-one, 4.83 g
(15.0 mmol) of benzophenone-3,3',4,4'-tetracarboxylic dianhydride,
and 80 ml ethylene glycol dimethyl ether. The mixture is stirred at
80.degree. C. for 12 hours. Solvent is evaporated to give 15 g of
light brown viscous oil, a mixture of the title compounds.
Example 16
1-{3,3-Bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]propyl}succinate
##STR00030##
[0223] {3,3-Bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]propanol is
prepared from 3,3-diphenylpropyl acetate by Friedel-Crafts
acylation, bromination, and hydrolysis according to the method of
Example 27. The alcohol is dissolved in 1,2-dimethoxyethane and
reacted with succinic anhydride and pyridine according to the
method of Example 10 to give the title compound.
Example 17
Methyl
3-[(2-{2-[4-(2-Hydroxy-2-methylpropionyl)phenoxy]ethoxycarbonyl}eth-
yl)(3-[(2-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxydimethoxysilylp-
ropyl)]amino]propionate
##STR00031##
[0225] 3-Aminopropyltrimethoxysilane (11.05 g, 61.7 mmol) and
methanol (20 ml) are stirred together for 30 minutes at room
temperature. To the mixture is added 41.46 g (482 mmol) of methyl
acrylate. The reaction mixture is heated overnight in a 30.degree.
C. oil bath. The reaction mixture is concentrated at reduced
pressure to give 21.50 g of crude methyl
3-[(2-methoxycarbonylethyl)-(3-trimethoxysilylpropyl)amino]propion-
ate, a yellow viscous oil. A mixture of the crude product,
1-[4-(2-hydroxyethyoxy)phenyl]-2-hydroxy-2-methylpropan-1-one
(26.85 g, 119.7 mmol) and 1,2-dimethoxyethane (80 ml) is heated in
an oil bath at 85.degree. (bath temperature). Zirconium(IV)
acetylacetonate (1.16 g, 2.38 mmol) is added, and the mixture is
stirred at 85.degree. C. overnight and then at room temperature for
24 hours. Solvent is evaporated, and approximately one-half of the
crude product is passed through a silica gel column with 5:1
chloroform:methanol as eluent to obtain 15.74 g of the title
compound, a yellow semisolid product.
Example 18
Methyl3-[(2-{2-[4-(2-Hydroxy-2-methylpropionyl)phenoxy]ethoxycarbonyl}ethy-
l)(3-[(2-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethoxydiethoxysilylpro-
pyl)]amino]propionate
##STR00032##
[0227] The procedure of Example 17 is repeated using
3-aminotriethoxysilane to obtain the title compound.
Example 19
5-[Bis-(3-trimethoxysilylpropyl)carbamoyl]-1-{2-[4-(2-hydroxy-2-methylprop-
ionyl)phenoxy]ethyl}ester3-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethy-
l}1,3,5-benzenetricarboxylate
##STR00033##
[0229] To a solution of 4.10 g (15.4 mmol) of
1,3,5-benzenetricarrboxylic acid chloride in 50 of
1,2-dimethoxyethane is added 6.72 g (30.0 mmol) of
1-[4-(2-hydroxyethyoxy)phenyl]-2-hydroxy-2-methylpropan-1-one. A
short time later, 3.76 g (47.5 mmol) of pyridine is added to the
reaction mixture. The reaction is monitored by IR spectroscopy. The
reaction mixture is stirred at room temperature for 40 minutes. To
two-thirds of the reaction mixture is added drop wise 5.41 g (15.8
mmol) of bis(trimethoxysilylpropyl)amine. The reaction mixture is
stirred for 20 minutes, filtered, and concentrated to give 12.32 g
of yellow oil. The title compound is a major component of the
reaction product.
Example 20
5-[(3-trimethoxysilylpropyl)carbamoyl]-1-{2-[4-(2-hydroxy-2-methylpropiony-
l)phenoxy]ethyl}ester3-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}1,-
3,5-benzenetricarboxylate
##STR00034##
[0231] Pyridine (3.72 g, 47.0 mmol) is added to a solution of 6.28
g (28.0 mmol) of
1-[4-(2-hydroxyethyoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2.51
g (14.0 mmol) of 3-aminopropyltrimethoxysilane and 25 ml of
tetrahydrofuran. The temperature is raised to 60.degree. C., and a
solution of 3.72 g (14.0 mmol) of 1,3,5-benzenetricarboxylic acid
chloride in 20 ml of tetrahydrofuran is added to the reaction
mixture drop wise over 10 minutes. The reaction mixture is stirred
at 60.degree. C. for 30 minutes, cooled to room temperature and
filtered. Solvent is evaporated to obtain 11.95 g of an oil
containing the title compound.
Example 21
2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl(3-triethoxysilylpropyl)car-
bamate
##STR00035##
[0233] A mixture of 5.89 g (26.3 mmol) of
1-[4-(2-hydroxyethyoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 5.40
g (21.8 mmol) of 3-triethoxysilylpropyl isocyanate and 0.012 g
(0.025 mmol) of zirconium(IV) acetonylacetonate in 50 ml of
1,2-dimethoxyethane is stirred at room temperature and then
60.degree. C. until reaction is complete. Solvent is evaporated to
give 11.32 g of product, a pale orange oil.
Example 22
{2-[4-(2-Hydroxy-2-methylpropionyl)phenoxy-ethyl}phosphonic
acid
##STR00036##
[0235] A solution of trimethylsilyl bromide (8.7 g, 0.057 moles) in
25 ml of dichloromethane is added drop wise at room temperature to
a mixture of 9.00 g (0.0285 mol) of
{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}phosphonic acid
dimethyl ester (Example 23) and 75 ml of dichloromethane. The
reaction mixture is stirred 5 hours at 25.degree. C. Solvent is
evaporated. Methanol (200 ml) is added, and the reaction mixture is
stirred at room temperature for 24 hours. Solvent is evaporated to
give 8 g of the title compound, a yellow oil.
Example 23
{2-[4-(2-Hydroxy-2-methylpropionyl)phenoxy]ethyl}phosphonic acid
dimethyl ester
##STR00037##
[0237] A solution of 43 g (0.128 mol) of carbon tetrabromide in 50
ml of dichloromethane is slowly added drop wise to a mixture of 14
g (0.062 mol) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one, 33 g
(0.128 mol) of triphenyl phosphine and 150 ml of dichloromethane.
The reaction is stirred overnight at room temperature. Solvent is
evaporated, and the resulting oil is purified by flash
chromatography on silica gel (8:2 heptane:ethyl acetate) to give 13
g (70% yield) of
1-[4-(2-bromoethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, a
yellow solid.
[0238] A mixture of 5.80 grams (0.0202 mol) of
1-[4-(2-bromoethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one and 6.27
g (0.0505 mol) of trimethyl phosphite is heated to 130.degree. C.
for 16 hours. The crude product is passed through a short column of
silica gel which is eluted with a mixture of 1:1 heptane:ethyl
acetate followed by methanol. Evaporation of solvent gives 3.5 g
(55% yield) of the title compound as a yellow oil.
Example 24
2-Hydroxy-2-methyl-1-{4-[2-(2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g][1,3-
,2]dioxaphosphocin-6-yloxy)ethoxy]phenyl}propan-1-one
##STR00038##
[0240] A mixture of 5.00 g (0.0223 moles) of
2,4,8,10-tetra-tert-butyl-6-chloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-
, 11.0 g (0.0225 moles) of
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one and 2.7
grams of triethylamine in 150 ml of dichloromethane is stirred at
room temperature for 24 hours. The solvent is evaporated, and the
crude material is recrystallized from a mixture of 95:5
acetonitrile:toluene to afford 9.5 g (63% yield) of a light pink
solid.
Example 25
{2-[4-(2-Hydroxy-2-methylpropionyl)phenyl]ethyl}phosphonic acid
##STR00039##
[0242] 2-Bromoethylbenzene (10.0 g, 0.0540 mol) is mixed with 6.6 g
(0.062 mol) of isobutyryl chloride and 100 ml of
1,2-dichlorobenzene. The mixture is cooled internally to 0.degree.
C., and 9.4 g (0.070 mol) of aluminum chloride is added portion
wise over 3 hours while keeping the reaction mixture at 0-5.degree.
C. The reaction mixture is stirred overnight, then poured into a
mixture of ice and concentrated hydrochloric acid. After stirring
for 30 minutes, the organic layer is washed with dilute
hydrochloric acid, sodium bicarbonate solution, and water, then
dried over sodium sulfate and concentrated to give 15.0 g of crude
1-[4-(2-bromoethyl)phenyl]-2-methylpropan-1-one.
[0243] A solution of 10 g of bromine in 25 ml of
1,2-dichlorobenzene is added drop wise at room temperature to 13.0
g (0.0509 mol) of crude
1-[4-(2-bromoethyl)phenyl]-2-methylpropan-1-one that is dissolved
in 100 ml of 1,2-dichlorobenzene. The reaction mixture is stirred
overnight, and then poured into a 5% sodium thiosulfate solution.
The mixture is stirred for 30 minutes, and the organic layer is
washed with 5% sodium thiosulfate solution, sodium bicarbonate
solution, and distilled water. The organic layer is passed through
a pad of silica gel and eluted with 9:1 heptane:ethyl acetate to
give, after concentration, 7.5 g (55% yield) of
2-bromo-1-[4-(2-bromoethyl)phenyl]-2-methylpropan-1-one.
[0244] A mixture of 5.0 g, 0.105 mol) of
2-bromo-1-[4-(2-bromo-ethyl)-phenyl]-2-methyl-propan-1-one, 0.60 g
(0.015 mol) of sodium hydroxide, 100 ml of ethanol and 50 ml of
1,2-dimethoxyethane is stirred at room temperature overnight. The
reaction mixture is concentrated and the crude product is dissolved
in ethyl acetate. The solution is washed with distilled water,
dried over sodium sulfate and concentrated to give 3.4 g of
1-[4-(2-bromoethyl)phenyl]-2-hydroxy-2-methylpropan-1-one.
[0245] A mixture of 10 g of
1-[4-(2-bromoethyl)phenyl]-2-hydroxy-2-methylpropan-1-one (0.037
moles) and 6.7 g (0.041 mol) of triethyl phosphite is heated
externally at 140.degree. C. for 24 hours. The reaction mixture is
distilled to give 12.1 g of
2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethyl}phosphonic acid
dimethyl ester. The ester is dissolved in 50 ml of dichloromethane,
and a solution of 6.2 g (0.0405 mol) of trimethylsilyl bromide in
10 ml of dichloromethane is added drop wise at room temperature.
The reaction mixture is stirred overnight. The reaction mixture is
concentrated, and methanol (200 ml) is added. The mixture is
stirred at temperature for 24 hours, and then concentrated to give
5.0 g of the title compound, a yellow oil.
Example 26
{3,3-Bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]propyl}phosphonic
acid
##STR00040##
[0247] 3,3-Diphenyl-1-bromopropanol (45 g, 99% yield) is prepared
from the reaction of 35 g (0.164 mol) of 3,3-diphenyl-1-propanol,
71 g (0.214 mol) of carbon tetrabromide and 56 g (0.214 mol) of
triphenylphosphine following the procedure of Example 23. The
bromide is reacted with 38.4 g (0.359 mol) of isobutyryl chloride
and 54.4 g (0.408 mol) of aluminum chloride according to the
procedure of Example 25 to give 12.8 g (19% yield) of
1-{4-[3-bromo-1-(4-isobutyrylphenyl)propyl]phenyl}-2-methylprop-
an-1-one. This product is then reacted with bromine followed by
sodium hydroxide and a catalytic amount of tetrabutylammonium
bromide, according to the procedure of Example 25, to give 5.0 g of
1-(4-{3-bromo-1-[4-(2-hydroxy-2-methylpropionyl)phenyl]propyl}phenyl)-2-h-
ydroxy-2-methylpropan-1-one.
[0248]
1-(4-{3-Bromo-1-[4-(2-hydroxy-2-methylpropionyl)phenyl]propyl}pheny-
l)-2-hydroxy-2-methylpropan-1-one (5.0 g, 0.0112 moles) is reacted
with 4.6 grams of triethyl phosphite following the procedure of
Example 23 to give 5.7 g (98% yield) of
{3,3-bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]propyl}phosphonic
acid dimethyl ester, a yellow oil. The ester is reacted with
trimethylsilyl bromide in chloroform and methanol, following the
procedure of Example 22, to give 5.0 g of the title compound, an
amorphous solid.
Example 27
3-[4-(2-Hydroxy-2-methylpropionyl)phenyl]-3-phenylpropanoic
acid
##STR00041##
[0250] A mixture of 80 g (0.333 mol) of
methyl3,3-diphenylpropanoate, 42.6 g (0.399 mol) of isobutyryl
chloride, and 600 mol of 1,2-dichlorobenzene is cooled to 4.degree.
C. Aluminum chloride (112 g, 0.832 mol) is added portion wise over
2 hours while the reaction temperature is kept between -5 and
5.degree. C. The reaction is kept within this temperature range for
7 hours, and then stirred at room temperature for 13 hours. The
reaction mixture is poured into a mixture of ice and concentrated
hydrochloric acid, and then stirred for 1 hour. The organic layer
is washed twice with dilute hydrochloric acid, and then
concentrated under vacuum to give 115 grams of crude product.
Purification by column chromatography on silica gel with 9:1
heptane:ethyl acetate as the eluent gives 69 g (60% yield) of
methyl 3-[4-(2-methylpropionyl)phenyl]-3-phenylpropanoate.
[0251] A solution of 29.4 g (0.184 mol) of bromine in 50 ml of
methylene chloride is added drop wise at room temperature to a
mixture of 52.0 g (0.168 mol) of methyl
3-[4-(2-methylpropionyl)phenyl]-3-phenylpropanoate in 250 ml of
methylene chloride. A small exotherm is controlled using a water
bath. The mixture is stirred for 16 hours at room temperature. The
reaction mixture is poured into a 5% aqueous sodium thiosulfate
solution and stirred for 10 minutes. The organic layer is washed
twice with 5% aqueous sodium thiosulfate solution, once with 10%
sodium bicarbonate solution, dried over sodium sulfate, and
concentrated to give 64.0 grams (98% yield) of methyl
3-[4-(2-bromo-2-methylpropionyl)phenyl]-3-phenylpropanoate.
[0252] A mixture of 64.0 g (0.164 mol) of
3-[4-(2-bromo-2-methylpropionyl)phenyl]-3-phenylpropanoate, 13.2 g
(0.328 mol) of sodium hydroxide, 70 ml of water, and 300 ml of
1,2-dimethoxyethane is heated at reflux for 16 hours. The reaction
is concentrated, and then acidified with 25 ml of 1.5 N
hydrochloric acid solution. Ethyl acetate (200 ml) is added, and
the organic layer is washed with distilled water, dried over sodium
sulfate, and concentrated. The crude product is passed through a
pad of silica gel with ethyl acetate as the eluent to give 44 g
(86% yield) of the title compound.
Example 28
1-[4-(2-{3-[Bis-(2-hydroxyethyl)amino]-2-hydroxypropoxy}ethyl)phenyl]-2-hy-
droxy-2-methylpropan-1-one
##STR00042##
[0254] The epoxide of
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one (see
Example 15) is prepared according to the procedure of Example 1A.
The epoxide is reacted with diethanolamine according to the
procedure of Example 2 to give the title compound.
Example 29
2-Hydroxy-1-(4-{2-[2-hydroxy-3-(3-triethoxysilyl-propylamino)propoxy]ethyl-
}phenyl)-2-methylpropan-1-one
2-Hydroxy-1-[4-(2-{2-hydroxy-3-[(2-hydroxy-3-{2-[4-(2-hydroxy-2-methylprop-
ionyl)phenoxy]ethyl}propyl)-(3-triethoxysilylpropyl)amino]-propoxy}ethyl)p-
henyl]-2-methylpropan-1-one
##STR00043##
[0256] The procedure of Example 1B is repeated with the epoxide of
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one (see
Example 15) to give a mixture of the title compounds.
Example 30
2-Hydroxy-1-(4-{2-[2-hydroxy-3-(2-hydroxyethylamino)propoxy]ethyl}phenyl)--
2-methylpropan-1-one
2-Hydroxy-1-[4-(2-{2-hydroxy-3-[(2-hydroxyethyl)-(2-hydroxy-3-{2-[4-(2-hyd-
roxy-2-methylpropionyl)phenoxy]ethyl}propyl)amino]propoxy}ethoxy)phenyl]-2-
-methylpropan-1-one
##STR00044##
[0258] The procedure of Example 3 is repeated with
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one
ethanolamine to give a mixture of the title compounds.
Example 31
3,3'-Bis-{2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethoxycarbonyl}biphenyl-
-4,4'-dicarboxylic acid
3,4'-Bis-{2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethoxycarbonyl}biphenyl-
-4,4'-dicarboxylic acid
##STR00045##
[0260] The procedure of Example 10 is repeated with
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl-2-methylpropan-1-one (example
15) substituted for
2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl-2-methylpropan-1-one to
obtain a mixture of the title compounds.
Example 32
1-[4-(2-{3-[Bis-(3-silanyl-propyl)amino]-2-hydroxypropoxy}ethyl)phenyl]-2--
hydroxy-2-methylpropan-1-one
##STR00046##
[0262] The procedure of example 2 is repeated with
bis(triethoxysilylpropyl)amine substituted for diethanolamine to
give the title compound.
Example 33
2-Hydroxy-2-(4-methoxybenzoyl)cyclohexanecarboxylic
acid(3-silanyl-propyl)-amide
##STR00047##
[0264] 3-Aminopropyltriethoxysilane (22.14 g, 0.100 mol) is added
to a solution of 26.03 g (0.100 mol) of
6-(4-methoxy-benzoyl)-7-oxa-bicyclo[4.2.0]octan-8-one in methylene
chloride. The reaction mixture is heated at reflux for several
hours and monitored by thin layer chromatography. Upon completion
of the reaction, solvent is evaporated to obtain the title
compound.
Example 34
2-Hydroxy-2-(4-methoxy-benzoyl)cyclohexanecarboxylic acid
bis(2-hydroxyethyl)amide
##STR00048##
[0266] A solution of 26.03 g (0.100 mol) of
6-(4-methoxy-benzoyl)-7-oxa-bicyclo[4.2.0]octan-8-one in 200 ml of
methylene chloride is added to 10.5 g (0.100 mol) of diethanolamine
and 32 ml of N,N-diisopropylethylamine. The reaction mixture is
heated at reflux for several hours and monitored by thin layer
chromatography. Upon completion of the reaction, the mixture is
cooled and poured into 1N hydrochloric acid solution. The organic
layer is washed with water, dried over anhydrous sodium sulfate,
and concentrated to give the title compound.
Example 35
2-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}dihydrogen1,2,4-benzene-
tricarboxylate
1-{2-[4-(2-hydroxy-2-methylpropionyl)phenoxy]ethyl}dihydrogen1,2,4-benzene-
tricarboxylate
##STR00049##
[0268] The procedure of Example 6 is repeated with
1,2,4-benzenetricarboxylic acid anhydride to give a mixture of the
title compounds.
Example 36
2,4-Bis[{2-[4-(2-hydroxy-2-methyl-propionyl)phenoxy]ethyl}carbonyl]benzene-
-1,5-dicarboxylic acid
1,4-Bis[{2-[4-(2-hydroxy-2-methyl-propionyl)phenoxy]ethyl}carbonyl]benzene-
-1,5-dicarboxylic acid
##STR00050##
[0270] The procedure of Example 9 is repeated with
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl-2-methylpropan-1-one (example
15) to give a mixture of the title compounds.
Example 37
2-{2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethyl}dihydrogen1,2,4-benzenet-
ricarboxylate
1-{2-[4-(2-hydroxy-2-methylpropionyl)phenyl]ethyl}dihydrogen1,2,4-benzenet-
ricarboxylate
##STR00051##
[0272] A mixture of the title compounds is prepared by from the
reaction of 20.8 g (0.100 mol) of
2-hydroxy-1-[4-(2-hydroxyethyl)phenyl-2-methylpropan-1-one (Example
15), 18.2 g (0.0947 mol) of 1,2,4-benzenetricarboxylic anhydride
and 7.5 g (0.0948 mol) of pyridine in 1,2-dimethoxyethane at
70.degree. C. until the reaction is complete, followed by
evaporation of the solvent.
Example 38
3,3'-Bis-{2-[4-((1-hydroxycyclohexyl)carbonyl)phenyl]ethoxycarbonyl}biphen-
yl-4,4'-dicarboxylic acid
4,3'-Bis-{2-[4-((1-hydroxycyclohexyl)carbonyl)phenyl]ethoxycarbonyl}biphen-
yl-3,4'-dicarboxylic acid
4,4'-Bis-{2-[4-((1-hydroxycyclohexyl)carbonyl)phenyl]ethoxycarbonyl}biphen-
yl-3,4'-dicarboxylic acid
##STR00052##
[0274] The reaction product, a mixture of three isomers, is
obtained by stirring 4.96 g (20 mmol) of
4-(2-hydroxyethoxy)phenyl1-hydroxy-cyclohexyl ketone, 2.94 g (10
mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1.58 g
(20 mmol) of pyridine in 80 ml of 1,2-dimethoxyethane at 80.degree.
C. until reaction is complete. Solvent is evaporated, the residue
dissolved in 100 ml methylene chloride, washed with 100 ml 0.4N
HCl, the organic layer concentrated and then dissolved in 200 ml
ethyl acetate. The solution is washed with 170 ml water until pH 6,
dried with MgSO.sub.4, and solvent removed to give 5.87 g (74.2%)
of a yellow-brown liquid: Mass spectrum: m/z 791.4 (M+H).sup.+.
Example 39
3,3'-Bis[{2-[4-((1-hydroxycyclohexyl)carbonyl)phenyl]ethoxy]carbony}lbenzo-
phenone-4,4'-dicarboxylic acid
3,4'-Bis[{2-[4-((1-hydroxycyclohexyl)carbonyl)phenyl]ethoxy]carbonyl}benzo-
phenone-4',3-dicarboxylic acid
4,4'-Bis[{2-[4-((1-hydroxycyclohexyl)carbonyl)pheny]ethoxy]carbonyl]benzop-
henone-3,3'-dicarboxylic acid
##STR00053##
[0276] To 3,3'4,4'-benzophenonetetracarboxylic dianhydride(2.50 g,
7.75 mmol) and 4-(2-hydroxyethoxy)phenyl1-hydroxy-cyclohexyl ketone
(3.70 g, 14.9 mmol) is added 50 ml of dimethoxyethane and pyridine
(1.20 g, 15 mmol). The mixture is stirred at 50.degree. C. until
the reaction is complete by tlc. Solvent is evaporated and 100 ml
ethyl acetate added to dissolve the residue, followed by successive
washes with 80 ml 1.5N HCl solution and 80 ml water. The organic
layer is dried with MgSO.sub.4, filtered, and solvent removed to
give 7.84 g light brown liquid: Mass spectrum: m/z 819
(M+H).sup.+
Example 40
3-[4-((1-hydroxycyclohexyl)carbonyl))phenyl]-3-phenylpropanoic
acid
##STR00054##
[0278] Step 1: A mixture of 47 9 (0.20 mol) of methyl
3,3-diphenylpropanoate, 60 g (0.409 mol) of cyclohexanecarbonyl
chloride, and 400 mol of 1,2-dichlorobenzene is cooled to 5.degree.
C. Aluminum chloride (104.5 g, 0.7836 mol) is added portionwise
with stirring over 2 hours while the reaction temperature is kept
between -5 and 8.degree. C. The reaction is stirred within this
temperature range for 20 hours, and then the reaction mixture is
poured into a mixture of ice and concentrated hydrochloric acid
(260 ml HCl+500 g ice), and stirred for 1 hour. The organic layer
is washed twice with dilute hydrochloric acid and once with water,
then concentrated under vacuum to give 98.59 grams of a light brown
liquid, 48.05 g. of which is purified by column chromatography on
silica gel, 8:2 heptane:ethyl acetate as eluent giving 11.02 g of
methyl3-phenyl-3-[4-(cyclohexylcarbonyl)phenyl]propionate as a
light brown liquid: Mass spectrum:m/z 351.2 (M+H).sup.+.
[0279] Step 2: A solution of 7.32 g (44.5 mmol) of bromine in 10 ml
of methylene chloride is added dropwise at room temperature to a
mixture of 10.18 g (37.10 mmol) of
methyl3-phenyl-3-[4-(cyclohexylcarbonyl)phenyl]propionate in 250 ml
of methylene chloride. The mixture is stirred for 16 hours at room
temperature after which the reaction mixture is poured into a 5%
aqueous sodium thiosulfate solution and stirred for 10 minutes. The
organic layer is washed twice with 5% aqueous sodium thiosulfate
solution, once with 10% sodium bicarbonate solution, dried over
sodium sulfate, and concentrated to give 8.19.0 g (62.5%) of
methyl3-phenyl-3-[4-((1-bromocyclohexyl)carbonyl)phenyl]propionate.
Mass spectrum: m/z 429.1 (M+H).sup.+.
[0280] Step 3: A mixture of 8.19 g (23.2 mmol) of
methyl3-phenyl-3-[4-((1-bromocyclohexyl)carbonyl)phenyl]propionate,
1.87 g (46.4 mmol) of sodium hydroxide, 10 ml of water, and 45 mL
of 1,2-dimethoxyethane is heated at reflux for 16 hours. The
reaction is concentrated and acidified with 25 ml of 1.5 N
hydrochloric acid solution. Ethyl acetate (200 ml) is added, and
the organic layer is washed with distilled water, dried over sodium
sulfate, and concentrated. The crude product is passed through a
pad of silica gel with ethyl acetate as the eluent to give 6.52 g
of the title compound. Mass spectrum: m/z 353.2
Example 41
4-(2-Hydroxyethyl)phenyl1-hydroxy-cyclohexyl ketone
##STR00055##
[0282] Step 1: Four hundred milliliters of methylene chloride is
cooled to 2.degree. C., and then aluminum chloride (160 g, 1.20
mol) is added while the temperature is kept between -5 and
8.degree. C. Cyclohexanecarbonyl chloride (75.08 g, 0.512 mol ) is
added dropwise to the solution. The reaction is kept within this
temperature range with mechanical stirring for 45 minutes, and then
82.8 g, (0.505 mol) of 2-phenyl-ethyl acetate is added dropwise to
the mixture, the temperature remaining between -5.degree. C. to
-8.degree. C. The reaction is stirred within this temperature range
for 20 hours, after which the reaction mixture is poured into a
mixture of ice and concentrated hydrochloric acid (300 ml HCl+700 g
ice), and stirred for 1 hour. The organic layer is washed with
2.times.250 ml water, dried, and concentrated under vacuum to give
116.12 g of a light brown liquid, 52.30 g of which is purified by
column chromatography on silica gel with 7:3 heptane:ethyl acetate
as the eluent giving 20.75 g of 4-(2-acetyloxyethyl)phenyl
cyclohexyl ketone as a light brown liquid,: Mass spectrum: m/z
275.2 (M+H).
[0283] Step 2: A solution of 14.0 g (88 mmol) of bromine in 15 ml
of methylene chloride is added dropwise at room temperature to a
mixture of 12.0 g (43.7 mmol) of 4-(2-acetyloxyethyl)phenyl
cyclohexyl ketone in 40 ml of methylene chloride. The mixture is
stirred for 16 hours at room temperature then poured into a 5%
aqueous sodium thiosulfate solution and stirred for 10 minutes. The
organic layer is washed twice with 5% aqueous sodium thiosulfate
solution, once with 10% sodium bicarbonate solution, dried over
sodium sulfate, and concentrated to give 15.81.0 g of
4-(2-acetyloxyethyl)phenyl1-bromo-cyclohexyl ketone: Mass spectrum:
m/z=353.25 (M+H).sup.+.
[0284] Step 3: A mixture of 8.19 g (23.2 mmol) of
4-(2-acetyloxyethyl)phenyl1-bromo-cyclohexyl ketone, 6.26g (15.65
mmol) of sodium hydroxide, 20 ml of water, and 50 ml of
1,2-dimethoxyethane is heated at reflux for 16 hours. The reaction
is concentrated, and then acidified with 25 ml of 1.5 N
hydrochloric acid. Ethyl acetate (200 ml) is added, and the organic
layer is washed with distilled water, dried over sodium sulfate,
and concentrated. The crude product is passed through a pad of
silica gel with ethyl acetate as the eluant to give 5.50 g of the
title compound which is further purified by recystallization. Mass
spectrum: m/z=249 (M+H).
Example 42
[0285] A 5% w/w solution of photoinitiator is dissolved in a primer
resin comprising 58% Ebecryl 8804, 14% HDODA and 28% IBOA. The
resin is applied over unprimed steel panels, cleaned with alcohol
prior to use, with a Bird bar at a wet thickness of 1.5 mil. Panels
are passed under a single Fusion lamp (600 W, VPS, H-Bulb and/or
V-Bulb) at a belt speed of 10 feet per minute.
[0286] Degree of cure is evaluated visually and by applying the mar
test. Dry adhesion is determined by using 3M tape #10 and a
standard cross-hatch tester with 2 mm razor spacing. The tape is
pressed onto the cross-hatch pattern on the panel, then quickly
pulled off. Adhesion is the ratio of squares where the coating has
not been pulled off by the tape to the total number of squares,
expressed as a percent. The cured panels are soaked in water at 22
degrees C. for 5 days. The panels are then rinsed in warm water and
patted dry with a soft paper cloth. The cross-hatch test is
performed to give wet adhesion data. Results are summarized in
Table 1
TABLE-US-00001 TABLE 1 Adhesion data for exposed panels. % % con-
surface adhesion adhesion Entry Photoinitiator centration cure dry
wet 1 PI 1 5 pph not 35 15 recorded 2 Example 23 5 pph hard 63 13 3
Example 19 5 pph tacky 81 89 4 Example 18 5 pph hard 83 22 5 PI 2 5
pph hard 85 42 6 PI 3 5 pph hard 65 47 7 PI 4 5 pph hard 65 62 8
Example 17 5 pph hard 87 33 9 Example 17 5 pph hard 89 39 10
Example 7 5 pph hard 89 85 11 Example 19 5 pph slight tack 89 33 12
PI 5 5 pph hard 92 79 13 PI 6 5 pph hard 92 97 14 Example 4 3.3 pph
hard 94 31 15 Example 19 5 pph slight tack 94 94 16 Example 20 5
pph tacky 94 91 17 Example 22 5 pph tacky 100 69 18 Example 5 5 pph
slight tack 100 99 19 Example 6 5 pph not 100 89 recorded PI 1 is
20% by weight phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and
80% by weight 2-hydroxy-2-methyl-1-phenyl-1-propanone PI 2 is
Bis-[4-(2-hydroxy-2-methylpropionyl)phenyl]methane PI 3 is 70%
oligo [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]and
30% 2-hydroxy-2-methyl-1-phenyl propan-1-one PI 4 is
1-[-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsul-
fonyl)propan-1-one PI 5 is
2-hydroxy-1-[4-(2-hydroxy-ethoxy)phenyl]-2-methylpropan-1-one PI 6
is 50 weight % benzophenone and 50% weight % 1-hydroxycyclohxyl
phenyl ketone
* * * * *